JP5810560B2 - Disc stopper - Google Patents

Description

  The present invention relates to a disk stopper that is attached to a turntable that rotates an optical recording disk such as a CD, a DVD, or a BD, and prevents the disk from slipping or slipping.

  A sheet-like disc stopper made of high static friction rubber or thermoplastic elastomer is attached to a turntable of a drive that rotates an optical recording disc such as a CD, DVD, or BD, thereby preventing the optical recording disc from slipping or slipping. It has been done to prevent.

  Conventionally, as such a disk stopper, one made of a thermoplastic elastomer is known (Patent Document 1: Japanese Patent Laid-Open No. 2001-256746), and a primer layer, an adhesive layer and an adhesive layer are sequentially laminated on one side thereof. Have also been proposed (Patent Document 2: Japanese Patent Laid-Open No. 2003-82136).

  However, conventional disk stoppers formed of these thermoplastic elastomers have a large compression set, and their performance tends to deteriorate with long-term use. In particular, the turntable of a disk drive that rotates at high speed and is irradiated with light is likely to reach a high temperature exceeding 50 ° C. Under severe conditions such as being exposed to a compressed state for a long time at such a high temperature, compression set As a result, so-called “sagging” is likely to occur, which causes inconveniences such as rotational misalignment, slip, and poor rotation.

JP 2001-256746 A JP 2003-82136 A

  The present invention has been made in view of the above circumstances, has a small compression set, good durability, and stable optical recording discs on a turntable without causing inconveniences such as rotational deviation, slip, and rotation failure. It is an object of the present invention to provide a disk stopper that can be rotated in a rotating manner.

  As a result of intensive studies to achieve the above object, the present inventor forms a grip layer having high static friction on one side of the base film made of a hard resin film and forms an adhesive layer on the other side. In manufacturing the disk stopper, the grip layer is formed of an ultraviolet curable resin, so that the compression set is small and exhibits excellent durability without causing inconveniences such as rotational deviation, slip, and rotation failure. The present invention has been completed by finding that a high-performance disk stopper capable of performing stable rotational running can be obtained, and that the following additional advantages can be obtained.

Advantage 1: Good adhesiveness can be obtained with respect to a base film such as PET, which has conventionally required a primary layer for good adhesion, and the primary layer can be omitted.
Advantage 2: A large-scale vulcanization process as in the case of using vulcanized rubber is not required, and a primary layer forming process is not required as described above.
Advantage 3: Curing is completed in a short time by UV irradiation, and high production efficiency can be expected.
Advantage 4: By applying UV curable resin to the shape of use such as ring shape and curing by UV irradiation, it is possible to easily obtain a product of use shape, and used after laminating the grip layer on the front surface of the base film There is almost no waste of material compared to punching into a shape.
Advantage 5: Further, by applying UV curable resin in the form of dots and curing by UV irradiation to form a grip layer as many points, the material used can be further reduced and the curing time can be shortened.

In addition, as a result of further studies on the ultraviolet curable resin, the present inventor has found the ultraviolet curable resin of the following claims 1 to 6 as an ultraviolet curable resin that can achieve the object of the present invention better. Accordingly, the present invention provides a disc stopper of the following claims 1-6.

［ただし、式中、Ｒ ¹ は（メタ）アクリロイル基およびビニル基の少なくともいずれかの不飽和基を含有するモノオール化合物の脱水酸基残基、Ｒ ² は有機ジイソシアナート化合物の脱イソシアナート残基、Ｒ ³ は、数平均分子量１×１０ ³ 〜１×１０ ⁴ で環状基または分岐鎖状基を含有するポリエステルジオール化合物の脱水酸基残基であり、Ａはジアミン化合物の脱水素残基またはジオール化合物の脱水素残基、ｐおよびｒの各々は０〜７、ｑは０〜３、ただし、ｑ＝０のとき、１≦ｐ＋ｒ≦１０である。］
で表され、かつ数平均分子量が５×１０ ³ 〜５×１０ ⁴ である不飽和基含有ウレタンオリゴマーである請求項１記載のディスクストッパー。
請求項３：
上記（Ｄ）成分の不飽和基含有ウレタンオリゴマー（ただし、一般式（１）においてｑ＝０の場合）が、前記ポリエステルジオール化合物と、前記有機ジイソシアナート化合物とを重付加反応させてイソシアナート基を両末端に有する付加物を形成した後、該イソシアナート基に、前記モノオール化合物を付加して得られるものである請求項２記載のディスクストッパー。
請求項４：
上記（Ｄ）成分の不飽和基含有ウレタンオリゴマー（ただし、一般式（１）においてｑ≠０の場合）が、前記ポリエステルジオール化合物と前記有機ジイソシアナート化合物とを重付加反応させてイソシアナート基を両末端に有する付加物を形成した後、前記ジアミン化合物または前記ジオール化合物の末端の各々を、該付加物の片端のイソシアナート基に付加させ、該付加物の他の片端のイソシアナート基に、前記モノオール化合物を付加して得られるものである請求項２記載のディスクストッパー。
請求項５：
上記（Ｅ）カルボジイミド基を含む化合物が、粘度０．１〜１００Ｐａ・ｓの液状ポリカルボジイミド化合物である請求項１〜４のいずれか１項に記載のディスクストッパー。
請求項６：
上記（Ｆ）成分のモノマーとしてフェノキシエチルアクリレート、光重合開始剤として４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトンを含有する請求項１〜５のいずれか１項に記載のディスクストッパー。 Claim 1:
A grip layer having a high static friction property is formed on one side of a base film made of a hard resin film, and an adhesive layer is formed on the other side. The disc is affixed to the turntable and placed on the turntable. a disk stopper to prevent the deviation, the above-mentioned grip layer,
(D) 100 parts by mass of an unsaturated group-containing ester urethane oligomer,
(E) 0.01 to 10 parts by mass of a compound containing at least one carbodiimide group in the molecule, and
(F) At least one of a photopolymerization initiator, a crosslinking agent, and a monomer
A disk stopper formed of an ultraviolet curable resin composition containing
Claim 2:
The unsaturated group-containing ester urethane oligomer of the component (D) is represented by the following general formula (1):

[Wherein R ¹ is a dehydroxylated residue of a monool compound containing at least one of a unsaturated group of (meth) acryloyl group and vinyl group, and R ² is a residue of a deisocyanate of an organic diisocyanate compound. Group R ³ is a dehydroxylated residue of a polyester diol compound having a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ and containing a cyclic group or a branched group, and A is a dehydrogenated residue of a diamine compound or Each of dehydrogenated residues p and r of the diol compound is 0 to 7, q is 0 to 3, provided that 1 ≦ p + r ≦ 10 when q = 0. ]
The disk stopper according to claim 1, which is an unsaturated group-containing urethane oligomer having a number average molecular weight of 5 × 10 ^{3 to} 5 × 10 ⁴ .
Claim 3:
The unsaturated group-containing urethane oligomer of the component (D) (provided that q = 0 in the general formula (1)) is subjected to a polyaddition reaction between the polyester diol compound and the organic diisocyanate compound. 3. The disk stopper according to claim 2, wherein the disc stopper is obtained by forming an adduct having groups at both ends and then adding the monool compound to the isocyanate group.
Claim 4:
The unsaturated group-containing urethane oligomer of the component (D) (provided that q ≠ 0 in the general formula (1)) undergoes a polyaddition reaction between the polyester diol compound and the organic diisocyanate compound to generate an isocyanate group. Are formed at both ends, and then each of the diamine compound or each of the ends of the diol compound is added to an isocyanate group at one end of the adduct, and is added to an isocyanate group at the other end of the adduct. The disk stopper according to claim 2, which is obtained by adding the monool compound.
Claim 5:
The disk stopper according to any one of claims 1 to 4, wherein the compound (E) containing a carbodiimide group is a liquid polycarbodiimide compound having a viscosity of 0.1 to 100 Pa · s.
Claim 6:
6. The phenoxyethyl acrylate as a monomer of the component (F) and 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone as a photopolymerization initiator. Disc stopper described in 1.

Furthermore, as a result of investigating a more preferable aspect of the configuration other than the ultraviolet curable resin, a disk stopper according to claims 7 to 10 described below was found.
Claim 7 :
The disk stopper according to any one of claims 1 to 6, wherein the hard resin film forming the base film is a polyethylene terephthalate (PET) film, a polypropylene (PP) film, or a polyethylene (PE) film.
Claim 8 :
The disk stopper according to any one of claims 1 to 7, wherein the adhesive layer is an acrylic double-sided adhesive tape.
Claim 9 :
The disk stopper according to any one of claims 1 to 8, wherein the grip layer is formed by applying the ultraviolet curable resin in a predetermined shape on a base film and irradiating with ultraviolet rays.
Claim 10 :
The said grip layer is many dot-shaped grip layers which apply | coated the said ultraviolet curing resin in the shape of a dot on the base film, and were hardened | cured by irradiating with an ultraviolet-ray, The any one of Claims 1-9. Disc stopper.

  That is, according to the disk stopper of the present invention, the compression set of the grip layer is small, and the optical recording disk can be stably rotated without lowering the grip performance even when used at a high temperature for a long period of time. It is excellent in durability.

  In addition, the primary layer for bonding the grip layer and the base film can be omitted, and it can be easily cured by ultraviolet irradiation, the grip layer forming process can be simplified, and the grip The layer shape can be formed into a final product shape or a dot shape relatively easily, and the material cost is excellent.

It is a schematic sectional drawing which shows an example of the disk stopper concerning this invention. It is a schematic sectional drawing which shows the other example of the disk stopper concerning this invention. It is a schematic plan view which shows the disk stopper.

  For example, as shown in FIG. 1, the disk stopper of the present invention forms a grip layer 2 having high static friction on one surface side of a base film 1 made of a hard resin film and forms an adhesive layer 3 on the other surface side. In such a disk stopper, in the present invention, the grip layer 2 is formed of an ultraviolet curable resin.

  The hard resin film forming the base film 1 is excellent in adhesiveness with a double-sided pressure-sensitive adhesive tape constituting the pressure-sensitive adhesive layer 3 and adheres well to the ultraviolet curable resin forming the grip layer 2. I just need it. Specific examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, polyethylene naphthalate (PEN) and the like. Particularly, polyethylene terephthalate (PET) film, polypropylene (PP film), polyethylene ( PE) film is preferably used.

  The thickness of the base film 1 is not particularly limited and is appropriately set depending on the use environment and the like, but is usually 10 to 1,000 μm, and particularly preferably 50 to 500 μm. .

  Further, the ultraviolet curable resin for forming the grip layer 2 is not particularly limited as long as it has a high coefficient of static friction, has an appropriate elasticity, and adheres well to the base film 1. Although not intended, in the present invention, the following ultraviolet curable resin compositions 1 to 3 are particularly preferably used.

・ UV curable resin composition (1)
(A) 20-90% by mass of a reactive polymer having a (meth) acryloyl group at the end;
(B) For 100 parts by mass of the total amount of (meth) acrylic acid ester monomer 80 to 10% by mass,
(C) An ultraviolet curable resin composition containing 0.1 to 10 parts by mass of a radical photopolymerization initiator.
・ UV curable resin composition (2)
(D) 100 parts by mass of an unsaturated group-containing ester urethane oligomer,
(E) 0.01 to 10 parts by mass of a compound containing at least one carbodiimide group in the molecule, and
(F) An ultraviolet curable resin composition containing at least one of a photopolymerization initiator, a crosslinking agent, and a monomer.
・ UV curable resin composition (3)
(G) a hydrogenated conjugated diene-aromatic vinyl copolymer containing a photocurable functional group,
(H) (meth) acrylate monomer, and
(I) An ultraviolet curable resin composition containing an aminoacetophenone photopolymerization initiator.
Hereinafter, the ultraviolet curable resin compositions (1) to (3) will be sequentially described.

[Ultraviolet curable resin composition (1)]
First, the said ultraviolet curable resin composition (1) is demonstrated.
The ultraviolet curable resin composition (1) is as described above.
(A) 20-90% by mass of a reactive polymer having a (meth) acryloyl group at the end;
(B) For 100 parts by mass of the total amount of (meth) acrylic acid ester monomer 80 to 10% by mass,
(C) An ultraviolet curable resin composition containing 0.1 to 10 parts by mass of a radical photopolymerization initiator.

（式中、Ａはジエン系オリゴマー鎖を示し、Ｒ¹は水素原子又はメチル基を示す。ｎは１又は２である。） Examples of the reactive polymer having a (meth) acryloyl group at the terminal of the component (A) include compounds represented by the following general formula (2).

(In the formula, A represents a diene oligomer chain, R ¹ represents a hydrogen atom or a methyl group, and n is 1 or 2.)

  As the compound represented by the general formula (2), specifically, a reactive polymer having a main skeleton of polybutadiene, particularly hydrogenated polybutadiene, and having a (meth) acryloyl group at the terminal is preferably used in the present invention. Specific examples include hydrogenated polybutadiene (meth) acrylate, hydrogenated polybutadiene di (meth) acrylate, urethane-modified hydrogenated polybutadiene (meth) acrylate, and hydrogenated polybutadiene di (meth) acrylate. In the present invention, “(meth) acrylate” means “acrylate or methacrylate”.

  Here, the urethane-modified hydrogenated polybutadiene (meth) acrylate is, for example, when both ends of a polymer obtained by subjecting a hydroxylated hydrogenated butadiene polymer and isocyanate to a high molecular weight by reacting with urethane are hydroxyl groups. When both ends of an acrylated polymer obtained by reacting both ends with a lower ester of acrylic acid (such as methyl acrylate) or a polymer having a high molecular weight are isocyanate groups, an acrylic ester monomer having hydroxyl groups at both ends ( 2-hydroxyethyl acrylate, etc.) and a polymer acrylated by reaction. In addition, the acrylated rate which acrylates a polymer terminal is not necessarily 100%.

  Further, as the compound represented by the general formula (2), a reactive polymer having polyisoprene, particularly hydrogenated polyisoprene as a main skeleton and having a (meth) acryloyl group at the terminal is also preferably used. Examples thereof include hydrogenated polyisoprene (meth) acrylate, hydrogenated polyisoprene (meth) acrylate, urethane-modified hydrogenated polyisoprene (meth) acrylate, and hydrogenated polyisoprene enedi (meth) acrylate. These can be used individually by 1 type or in combination of 2 or more types. In the ultraviolet curable resin composition (1), the component (A) preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000. There exists an advantage that hardened | cured material is low hardness as a weight average molecular weight is 1,000-100,000.

This compound of the above formula (2) is obtained by subjecting a (meth) acrylic acid lower alkyl ester and an oligomer chain terminal alcohol represented by the following general formula (3) to an ester exchange reaction in the presence of an ester exchange catalyst. The resulting reaction mixture can be produced by treating with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent.
A- [OH] n (3)
(In the formula, A and n are the same as above.)

  In the (meth) acrylic acid lower alkyl ester, the lower alkyl ester moiety preferably has 1 to 4 carbon atoms. Specific examples of the (meth) acrylic acid lower alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate and the like. Among these, methyl (meth) acrylate is preferable because it is inexpensive and has excellent versatility.

  In the above general formulas (2) and (3), the diene oligomer chain represented by A is an oligomer chain obtained by polymerizing a conjugated diene and, if necessary, another copolymerizable monomer, or this oligomer chain is hydrogenated. The oligomer chain | strand obtained by making it mention is mentioned. Examples of polymers constituting suitable diene oligomer chains include polyisoprene, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polychloroprene, poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol. , Poly- [epsilon] -caprolactone, and hydrogenated compounds thereof. In these, the polybutadiene which may be hydrogenated and the polyisoprene which may be hydrogenated are preferable. In the said General formula (2) and (3), n shows the number of the hydroxyl groups couple | bonded with the diene oligomer chain | strand which comprises said A.

  Moreover, the manufacturing method of the oligomer chain terminal alcohol represented by the said General formula (3) is not specifically limited, For example, a hydroxyl group is introduce | transduced into the polymer which comprises the said diene type oligomer chain by ethylene oxide or propylene oxide, etc. It can manufacture by the well-known method of these.

  The transesterification reaction between the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol represented by the general formula (3) is carried out in the presence of a transesterification catalyst. Preferable examples of the transesterification catalyst include titanium compounds such as tetraethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, tetramethoxy titanate, tetraethoxy titanate, titanium tetrachloride, titanium tetrabromide; lithium methylate, lithium ethyl Alkali metal alcoholates such as sodium, sodium methylate and sodium ethylate; alkaline earth metal alcoholates such as calcium methylate, calcium ethylate, magnesium methylate and magnesium ethylate; aluminum alcoholates such as aluminum methylate and aluminum ethylate Lithium hydroxide; boron halides such as boron trifluoride, boron trichloride, and boron tribromide. These can be used alone or in admixture of two or more. In these, a titanium compound and lithium hydroxide are preferable from a viewpoint of making a transesterification reaction advance efficiently.

  The amount of the transesterification catalyst is desirably 0.00001 mol or more, preferably 0.0001 mol or more per mol of the oligomer chain terminal alcohol, from the viewpoint of efficiently proceeding the transesterification reaction. From the viewpoint of cost reduction, yield improvement, waste reduction, and suppression of polymerization of (meth) acrylic acid lower alkyl ester, it is usually 0.1 mol or less, preferably 0.03 per mol of oligomer chain terminal alcohol. It is desirable that it be less than or equal to a mole. From these viewpoints, the amount of the transesterification catalyst is 0.00001 to 0.1 mol, preferably 0.0001 to 0.03 mol, per mol of oligomer chain terminal alcohol.

  The transesterification reaction of the above (meth) acrylic acid lower alkyl ester and the above general formula (3) oligomer chain terminal alcohol can be carried out in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbon compounds such as n-hexane, heptane, and octane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic carbon compounds such as benzene, toluene, xylene, and cumene. Hydrogen compounds; organic solvents such as ether compounds such as tetrahydrofuran, di-n-butyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether are listed. Of these, n-hexane is preferred. Although the usage-amount of a solvent is not specifically limited, Preferably it is 0-500 mass parts with respect to 100 mass parts of oligomer chain terminal alcohol, More preferably, it is 0-100 mass parts.

  From the viewpoint of suppressing the polymerization of the (meth) acrylic acid lower alkyl ester, when the transesterification reaction between the (meth) acrylic acid lower alkyl ester and the oligomer chain terminal alcohol represented by the general formula (3) is performed, It is preferable to stir the reaction system under an air stream or to use a polymerization inhibitor.

  As the polymerization inhibitor, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetamino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzooxy- 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N- N-oxy radical compounds such as oxyl; hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-4-methylphenol, 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 2 , 6-Di-t-butyl-N, N-dimethylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4-t-butyl Phenol compounds such as catechol, 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol); phenothiazine, N , N′-diphenyl-p-phenylenediamine, phenyl-β-naphthylamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, and other amine compounds Hydroxylamine compounds such as 1,4-dihydroxy-2,2,6,6-tetramethylpiperidine, 4-dihydroxy-2,2,6,6-tetramethylpiperidine; benzoquinone, 2,5-di-t; -Quinone compounds such as butyl hydroquinone; copper compounds such as ferrous chloride and copper dimethyldithiocarbamate And the like. These can be used alone or in admixture of two or more.

  Among the polymerization inhibitors, not only the (meth) acrylic acid lower alkyl ester but also the polymerization of the compound represented by the general formula (2) as the target compound (hereinafter referred to as the compound (2)) is effective. N-oxy radical compounds, phenol compounds, amino compounds, and hydroxylamine compounds are preferable. Among these, from the viewpoint of effectively suppressing polymerization of the (meth) acrylic acid lower alkyl ester and the compound (2), the N-oxy radical compound and the combined use of the N-oxy radical compound and the phenol compound are more preferable. preferable. In addition, the said polymerization inhibitor can be used together with another polymerization inhibitor. Thus, when the said polymerization inhibitor and another polymerization inhibitor are used together, the more superior polymerization inhibitory effect can also be acquired according to the synergistic effect by both combined use.

  The amount of the polymerization inhibitor used is from 5 to 5,000 mass ppm of (meth) acrylic acid lower alkyl ester, preferably 50 from the viewpoint of sufficiently exhibiting the polymerization inhibitory effect and obtaining compound (2) in high yield. It is desirable to be ˜3,000 mass ppm. The reaction temperature in the transesterification reaction is usually about 60 to 150 ° C., preferably the reflux temperature. Moreover, the reaction atmosphere in the transesterification reaction is preferably a gas containing air, oxygen gas, or oxygen gas, more preferably air or oxygen gas, from the viewpoint of suppressing polymerization of the (meth) acrylic acid lower alkyl ester. In the transesterification reaction, lower alcohol is by-produced as the transesterification proceeds. The by-produced lower alcohol is preferably removed from the reaction system as an azeotropic mixture with (meth) acrylic acid lower alkyl ester or reaction solvent.

  The end point of the transesterification reaction can be easily confirmed by the fact that the azeotropic mixture is no longer distilled. In addition, when the end point of the transesterification reaction is confirmed in more detail, it can be easily confirmed by introducing a protecting group having ultraviolet absorptivity into the residual hydroxyl group of the reaction mixture, for example, by high performance liquid chromatography. it can. Since the reaction time of the transesterification reaction varies depending on the reaction conditions and the like, it cannot generally be determined, but is usually about 5 to 30 hours.

  In this way, compound (2) is obtained. In order to increase the purity of the compound, the reaction mixture may be concentrated.

  Next, the obtained reaction mixture is treated with a solid adsorbent in the presence of a mixed solvent of a hydrophilic solvent and a lipophilic solvent. During this treatment, the catalyst contained in the reaction mixture is removed by the solid adsorbent, so that the purity of the compound (2) can be increased. Examples of the solid adsorbent include activated clay, activated carbon, silica gel, acidic ion exchange resin, and hydrotalcite. These can be used alone or in admixture of two or more. Among these, the combined use of silica gel and hydrotalcite and the combined use of acidic ion exchange resin and hydrotalcite are preferable because they are excellent in the catalyst removal effect.

  When the transesterification catalyst used in the transesterification reaction is an alkyl titanate such as tetraethyl titanate, tetraisopropyl titanate or tetra n-butyl titanate, or an alkoxy titanate such as tetramethoxy titanate or tetraethoxy titanate, a reaction mixture By adding water to the catalyst, the effect of removing the catalyst by the solid adsorbent can be enhanced. In this case, the amount of water is usually 0.05 to 20 parts by mass with respect to 100 parts by mass of the reaction mixture from the viewpoint of increasing the catalyst removal efficiency and suppressing hydrolysis of the generated compound (2). The degree, preferably 0.1 to 10 parts by mass is desirable.

  The amount of the solid adsorbent used is usually about 0.01 to 10 parts by mass per 100 parts by mass of the compound (2) contained in the reaction mixture, considering the adsorptivity of the catalyst and the subsequent filterability of the adsorbent. Preferably it is 0.05-5 mass parts.

  Moreover, the mixed solvent of the said hydrophilic solvent and lipophilic solvent expresses the effect of improving the contact efficiency of the catalyst and water contained in the compound (2). Here, the hydrophilic solvent means an organic solvent having a solubility in 100 parts by mass of water at 25 ° C. of 8 parts by mass or more. Further, the lipophilic solvent means an organic solvent capable of dissolving the oligomer chain terminal alcohol and the oligomer chain terminal (meth) acrylate.

  Examples of the hydrophilic solvent include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; and C 1 to C 1 such as methanol, ethanol, propanol, butanol, ethylene glycol, and glycerin. 4 water-soluble alcohols. These can be used alone or in admixture of two or more. Of these, acetone and tetrahydrofuran are preferred.

  Examples of the lipophilic solvent include aliphatic hydrocarbon compounds such as n-hexane, heptane, and octane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatics such as benzene, toluene, xylene, and cumene. Group hydrocarbon compounds; ethers such as di-n-butyl ether; and oil-soluble alcohols having 5 to 12 carbon atoms. These can be used alone or in admixture of two or more. Of these, n-hexane and toluene are preferred.

  The mass ratio of the hydrophilic solvent to the lipophilic solvent (hydrophilic solvent / lipophilic solvent) is usually 1 / (from the viewpoint of increasing the solubility of the oligomer chain terminal (meth) acrylate and the solubility of water in this solvent). It is about 99-30 / 70, preferably 3 / 97-10 / 90. The use amount of the mixed solvent of the hydrophilic solvent and the lipophilic solvent is as described above from the viewpoint of lowering the viscosity of the generated oligomer chain terminal (meth) acrylate and increasing the contact efficiency between the remaining catalyst and water. It is usually about 50 to 2,000 parts by mass, preferably 100 to 1,000 parts by mass, with respect to 100 parts by mass of the oligomer chain terminal alcohol represented by the general formula (3).

  The adsorption removal of the catalyst contained in the reaction mixture by the solid adsorbent can be performed, for example, by adding the solid adsorbent and the mixed solvent to the reaction mixture and then stirring. The treatment temperature for removing the catalyst is usually about 20 to 150 ° C., preferably 50 to 100 ° C., from the viewpoint of operability and thermal stability of the compound (2). The treatment time is usually about 1 to 30 hours, preferably 3 to 10 hours.

  After performing the adsorption treatment in this way, the solid adsorbent and impurities contained in the reaction mixture are removed by filtration. For the filtration, for example, pressure filtration, vacuum filtration, centrifugal filtration, or the like can be used. At that time, diatomaceous earth may be used as a filter aid to prevent addition by filtration. After filtration, by concentrating the obtained filtrate, impurities such as a decomposition product of the transesterification catalyst are distilled off, and the purity of the compound (2) can be further increased.

  Next, the (meth) acrylic acid ester monomer of the component (B) preferably has a molecular weight of less than 1,000, more preferably 150 to 600. Specific examples of (meth) acrylic acid ester monomers include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and diethylene glycol monoethyl ether. (Meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meta ) Acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, Octyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripylene glycol (meta ) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol acrylate, and the like. Of these, dicyclopentanyl acrylate, dicyclopentenyl acrylate and isobornyl acrylate are particularly preferably used.

  The blending ratio of the component (B) and the component (A) is 20 to 90% by mass of the component (A) and 80 to 10% by mass of the component (B), preferably 40 to 80% by mass of the component (A) ( B) 60-60 mass% of component, More preferably, it is 50-80 mass% of (A) component (B) 50-20 mass% of component. In this case, when the blending ratio of the component (B) is 10% by mass or more as described above, the adhesive strength of the composition becomes favorable, and when it is 80% by mass or less, the viscosity of the composition is increased. It is possible to prevent the resin from becoming too low and obtain good moldability.

  Next, as the radical photopolymerization initiator of the component (C), benzoin derivatives and benzyl ketals [for example, trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.], α -Hydroxyacetophenones [for example, Ciba Specialty Chemicals Co., Ltd., trade names: Darocur 1173, Irgacure 184, Irgacure 127], α-aminoacetophenones [eg, Ciba Specialty Chemicals Co., Ltd., trade name : Irgacure 907, Irgacure 369], α-aminoacetophenones and thioxanthones (for example, isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides [for example, manufactured by Ciba Specialty Chemicals Co., Ltd. Trade name: IRGACURE 819], and the like, as a hydrogen abstraction type, combined use of benzophenones and amines, and the like combination of thioxanthones and amines. Further, an intramolecular cleavage type and a hydrogen abstraction type may be used in combination. Of these, oligomerized α-hydroxyacetophenone and acrylated benzophenones are preferred. More specifically, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] [for example, Lamberti S. et al. p. A product, trade name: ESACURE KIP150, etc.], acrylated benzophenone [for example, trade name: Ebecryl P136, etc., manufactured by Daicel UCB Co., Ltd.], imide acrylate, and the like.

  In addition to these, the radical photopolymerization initiator of the component (C) includes 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl. -Phenyl-ketone, 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone mixture, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2, 4,6-trimethylbenzoylphenylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 2-methyl-1-[(4-methylthio) phenyl] -2-morpho Nopropan-1-one, benzoyl methyl ether, benzoyl ethyl ether, benzoyl butyl ether, benzoyl isopropyl ether, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1- Methylvinyl) phenyl] propanol oligomer, mixture of 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer and 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone , Methyl o-benzoylbenzoate and [4- (methylphenylthio) phenyl] phenylmethane can also be used.

  The blending amount of the component (C) is 0.1 to 10 parts by mass, preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). The

  In addition to the components (A), (B), and (C), the ultraviolet curable resin composition (1) may contain an inorganic filler and / or an organic thickener as necessary. By blending an inorganic filler and / or an organic thickener, the composition can have thixotropy and the moldability of the composition can be further improved.

Examples of the inorganic filler include silica (SiO ₂ ), alumina, titania, viscosity mineral, and the like, and among these, silica powder, hydrophobically treated silica powder, or a mixture thereof is preferable. More specifically, a silica fine powder pulverized by a dry method [for example, product name: Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.], a fine powder obtained by modifying this silica fine powder with trimethyldisilazane [for example, Japan Aerosil Co., Ltd., trade name: Aerosil RX300, etc.] and fine powder obtained by modifying the above silica fine powder with polydimethylsiloxane [for example, Nippon Aerosil Co., Ltd., trade name: Aerosil RY300, etc.]. The average particle diameter of the inorganic filler is preferably 5 to 50 μm, more preferably 5 to 12 μm, from the viewpoint of thickening and thixotropy.

  As the organic thickener, hydrogenated castor oil, amide wax or a mixture thereof is preferably used. More specifically, hydrogenated castor oil which is a hydrogenated product of castor oil (non-drying oil whose main component is ricinoleic acid) [for example, manufactured by Zude Chemy Catalyst Co., Ltd., trade name: ADVITROL100, manufactured by Enomoto Kasei Co., Ltd., product Name: Disparon 305 etc.] and high-grade amide wax which is a compound obtained by substituting hydrogen of ammonia with an acyl group [for example, trade name: Disparon 6500, etc., manufactured by Enomoto Kasei Co., Ltd.].

  When using these inorganic fillers and / or organic thickeners, the blending amount is preferably 0.3 to 15 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). More preferably, it is 1-10 mass parts. When the blending amount is 0.3 parts by mass or more, an appropriate height is obtained when the composition is applied, and the moldability becomes good. Moreover, the increase of the compression set of a hardened | cured material, the raise of hardness, and the fall of adhesive strength are suppressed as it is 15 mass parts or less.

  Furthermore, an appropriate amount of a terminal (meth) acrylate oligomer can be blended in the ultraviolet curable resin composition (1). By blending this terminal (meth) acrylate oligomer, the viscosity of the composition can be adjusted, and physically, the hardness is lowered, and Eb (elongation) and Tb (breaking strength) are improved. be able to. The terminal (meth) acrylate oligomer refers to an oligomer having an acryloyl group or a methacryloyl group at one end or both ends. The terminal (meth) acrylate oligomer is preferably a hydrocarbon oligomer, that is, a hydrogenated oligomer or a terminal (meth) acrylate hydrogenated oligomer, from the viewpoint of moisture permeability, weather resistance and heat resistance. The weight average molecular weight of the terminal (meth) acrylate oligomer is preferably 1,000 to 100,000, more preferably 10,000 to 50,000. When the weight average molecular weight is within this range, there are advantages that it is easy to handle as a liquid raw material and the cured product has low hardness.

  Examples of the terminal (meth) acrylate oligomer include polyester (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyol (meth) acrylate oligomers, and the like. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Alternatively, it can be modified with isocyanate and the terminal hydroxyl group can be esterified with acrylic acid. The polyol (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.

  A stabilizer may be further added to the ultraviolet curable resin composition (1) as necessary. As a stabilizer, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate] [for example, Ciba Specialty Chemicals Co., Ltd., trade name: IRGANOX245, Asahi Manufactured by Denka Kogyo Co., Ltd., trade name: ADK STAB AO-70, etc.], 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane [for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: ADK STAB AO-80, etc.] Etc.

  The amount of the stabilizer is not particularly limited, but is preferably 0.05 to 5 parts by mass, more preferably 100 parts by mass of the total of the component (A) and the component (B). Is 1 to 3 parts by mass.

  Furthermore, the ultraviolet curable resin composition (1) includes a terpene resin, a terpene phenol resin, a coumarone resin, a coumarone-indene resin, a petroleum hydrocarbon, and a rosin derivative within a range not impairing the object and effects of the present invention. It is possible to add known additives such as various tackifiers such as titanium black and colorants such as titanium black.

[UV curable resin composition (2)]
Next, the ultraviolet curable resin composition (2) will be described.
The ultraviolet curable resin composition (2) is as described above.
(D) 100 parts by mass of an unsaturated group-containing ester urethane oligomer,
(E) 0.01 to 10 parts by mass of a compound containing at least one carbodiimide group in the molecule, and
(F) An ultraviolet curable resin composition containing at least one of a photopolymerization initiator, a crosslinking agent, and a monomer.

Examples of the unsaturated group-containing ester urethane oligomer (D) include those represented by the following general formula (1).

R ¹ in the general formula (1) is a dehydroxylated residue of a monool compound containing an unsaturated group of at least ^one of a (meth) acryloyl group and a vinyl group. Preferred examples of the monool compound include hydroxyalkyl (meth) acrylate and hydroxyalkyl vinyl. For example, diethylene glycol (meth) acrylate, dipropylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, triethylene glycol (meta ) Acrylate and polyethylene glycol (meth) acrylate. This R ¹ is particularly preferably a hydroxyl group-removed residue of a monool compound of either hydroxyalkyl (meth) acrylate or hydroxyalkyl vinyl ether, for example, a hydroxyl group-removed residue such as hydroxyethyl acrylate or hydroxymethyl vinyl ether. It is preferable that

R ² in the general formula (1) is a deisocyanate residue of the organic diisocyanate compound. For example, alkylene groups such as methylene group, ethylene group, propylene group, butylene group and hexamethylene group, cycloalkylene groups such as cyclohexylene group, arylene groups such as phenylene group, tolylene group and naphthylene group, xylylene groups and the like are included. Here, the alkyl group may be linear, branched or cyclic. Organic diisocyanate compounds include isophorone diisocyanate, hexamethylene diisocyanate, norbornane diisocyanate, tolylene diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated xylates. Preferred examples include range isocyanate, hydrogenated diphenylmethane diisocyanate and diphenylmethane diisocyanate.

R ³ in the general formula (1) is a dehydroxylated residue of a polyester diol compound having a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ and containing a cyclic group or a branched chain group. More specifically, R ³ is a dehydroxylated residue of the polyester diol compound in which a cyclic group-containing dicarboxylic acid and a diol are condensed, or a polyester diol compound in which a cyclic group-containing dicarboxylic acid anhydride is modified by reacting with the diol. Dehydroxylated residues are preferred.

Examples of the cyclic group-containing dicarboxylic acid or acid anhydride constituting R ³ include phthalic acid, phthalic anhydride, pyromellitic acid, pyromellitic anhydride, isophthalic acid, trimellitic acid, trimellitic anhydride, tetrahydro Examples thereof include phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride and the like. Moreover, you may use these in mixture of multiple types. Examples of the diol constituting R ³ include ethylene glycol, propylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,2-propanediol, and 1,3-propanediol. 1,4-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, bisphenol A, tetraethoxyxylate, 2,2-thiodiethanol, acetylene-type diol, hydroxy-terminated polybutadiene, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-bis (2-hydroxyethoxy) Cyclohexane, trimethylene glycol Tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornylene glycol, 1,4-benzenedimethanol, 1,4-benzeneethanol, 2,4- Dimethyl-2-ethylenehexane-1,3-diol, 2-butene-1,4-diol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol And 3-methyl-1,5-pentanediol.

  In general formula (1), A is a dehydrogenation residue of a diamine compound or a dehydrogenation residue of a diol compound. More specifically, examples of A include diaminopropane, diaminobutane, nonanediamine, isophoronediamine, hexamethylenediamine, hydrogenated diphenylmethanediamine, bisaminopropyl ether, bisaminopropylethane, bisaminopropyldiethylene glycol ether, and bisaminopropyl. Dehydrogenated residues of diamine compounds selected from polyethylene glycol ether, bisaminopropoxyneopentyl glycol, diphenylmethanediamine, xylylenediamine, toluenediamine, and both-terminal amino group-modified silicones, and ethylene glycol, propylene glycol, polyethylene glycol, polypropylene Glycol, butylene glycol, polytetramethylene glycol, pentanediol, hexane All, it is preferable dehydrogenation residue of a diol compound selected from the hydroxyl groups at both ends modified silicone, and a carboxyl group-containing diol.

  This (D) unsaturated group-containing ester urethane oligomer can be preferably produced by the following method. That is, the unsaturated group-containing urethane oligomer when q = 0 in the general formula (1) has an isocyanate group at both ends by polyaddition reaction of the polyester diol compound and the organic diisocyanate compound. After forming an adduct, the monool compound can be added to the isocyanate group.

  Further, the unsaturated group-containing urethane oligomer in the case of q ≠ 0 in the general formula (1) is an addition having an isocyanate group at both ends by polyaddition reaction of the polyester diol compound and the organic diisocyanate compound. After forming the product, each of the diamine compound or each end of the diol compound is added to an isocyanate group at one end of the adduct, and the monool compound is added to the isocyanate group at the other end of the adduct. It can be obtained in addition.

The number average molecular weight of the unsaturated group-containing urethane oligomer obtained by the above method is preferably 5 × 10 ^{3 to} 5 × 10 ⁴ , but 5 × as long as it does not depart from the objects and effects of the present invention. 10 ⁴ may be exceeded.

  Next, the compound containing a carbodiimide group as component (E) (hereinafter sometimes simply referred to as “carbodiimide compound”) has a carbodiimide group represented by [—N═C═N—] in the molecule. It is necessary to have at least one and react with carbodiimide active hydrogen (carboxylic acid, amine, alcohol, thiol, etc.). The function of this carbodiimide compound is to react with the hydroxyl group / carboxyl group remaining in the unsaturated group-containing ester urethane oligomer of component (D), which is considered to promote hydrolysis at the initial stage after addition, to cause hydrolysis. It is then controlled and then added to the ester bond cleaved by the hydrolysis reaction to act as a recombination and repair. However, low molecular weight substances such as monocarbodiimide are easily thermally decomposed during processing, have environmental pollution due to generation of an irritating odor component, and decrease in the effect of addition due to vaporization. It is preferable to use polycarbodiimide.

  As the carbodiimide compound (including polycarbodiimide compound) having one or more carbodiimide groups in the molecule (E), those synthesized by a generally well-known method can be used. Examples of compounds that can be synthesized by subjecting various polyisocyanates to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or higher are used. be able to.

  Examples of the organic diisocyanate that is a synthetic raw material in the production of a polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate. 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2, , 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophoro Illustrate diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. Can do.

  Moreover, in the case of the said polycarbodiimide compound, a polymerization reaction can be stopped on the way by cooling etc., and it can control to a suitable polymerization degree. In this case, the terminal is isocyanate. Furthermore, in order to control the degree of polymerization to an appropriate degree, there is a method in which all or part of the remaining terminal isocyanate is sealed using a compound that reacts with the terminal isocyanate of the polycarbodiimide compound, such as monoisocyanate. By controlling the degree of polymerization, compatibility with the polymer and storage stability can be increased, which is preferable in terms of quality improvement.

Examples of the monoisocyanate for sealing the end of such a polycarbodiimide compound and controlling the degree of polymerization thereof include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like. be able to. Further, the end-capping agent that seals the end of the polycarbodiimide compound and controls the degree of polymerization thereof is not limited to the above-mentioned monoisocyanate, and is an active hydrogen compound that can react with isocyanate, for example, (i) An aliphatic, aromatic or alicyclic compound having an —OH group, methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether; (ii) = NH group diethylamine with, dicyclohexylamine; butylamine with (iii) -NH ₂ group, cyclohexylamine; succinic acid having a (iv) -COOH group, benzoic acid, cyclohexane acid, ethyl mercaptan with (v) -SH groups, Arirumerukaputa , Thiophenol; can be exemplified (vii) acetic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and the like; compound with (vi) an epoxy group.

The decarboxylation condensation reaction of the organic diisocyanate is performed in the presence of a suitable carbodiimidization catalyst. Examples of the carbodiimidization catalyst that can be used include organic phosphorus compounds, organometallic compounds (general formula M- (OR) ₄ [M is titanium (Ti), sodium (Na), potassium (K), vanadium (V), tungsten (W), hafnium (Hf), zirconium (Zr), lead (Pb), manganese (Mn), nickel (Ni), calcium (Ca), barium (Ba), etc., wherein R represents an alkyl group or aryl group having 1 to 20 carbon atoms] is preferred, particularly from the standpoint of activity Phosphorene oxides are preferable for organic phosphorus compounds, and alkoxides of titanium, hafnium, and zirconium are preferable for organic metal compounds.

  Preferred carbodiimide compounds of component (E) obtained as described above include 4,4′-dicyclohexylmethane carbodiimide, tetramethylxylylene carbodiimide, N, N-dimethylphenylcarbodiimide, N, N′-di-2, Examples include 6-diisopropylphenylcarbodiimide. Although it will not specifically limit if it is a carbodiimide compound which has a 2 or more carbodiimide group in a molecule | numerator, From the point of a hue, safety | security, and stability, an aliphatic polycarbodiimide compound is preferable.

  Further, in order to facilitate mixing and dispersion with the component (D), it is preferably liquid, and from the point of being liquid, the viscosity of the component (E) is preferably 0.1 to 100 Pa · s, 0 5 to 10 Pa · s is more preferable. By setting the viscosity of component (E) within the above range, vaporization of component (E), which is a problem in the working environment, can be suppressed, and mixing and dispersion can be facilitated. Such a liquid carbodiimide compound can also be obtained as a commercial product, and examples thereof include a product name “Elastostab H01” viscosity 1-6 Pa · s manufactured by Nisshinbo Co., Ltd. In addition, the said viscosity of (E) component is measured based on JISZ8803 at the measurement temperature of 25 degreeC.

  The compounding amount of the carbodiimide compound as the component (E) is in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (D), preferably in the range of 0.01 to 5 parts by mass. A range of 0.1 to 3.0 parts by mass is particularly preferable. By making a compounding quantity into the said range, the hydrolysis resistance of the easily hydrolyzable resin which has an ester group can be improved.

  Moreover, at least one of a photopolymerization initiator, a crosslinking agent, and a monomer is added to the ultraviolet curable resin composition (2) as the component (F). In this case, the photopolymerization initiator may be either an intramolecular cleavage type or a hydrogen abstraction type. Examples of the intramolecular cleavage type include benzoin derivatives, benzyl ketals [for example, Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 651], α-hydroxyacetophenones [for example, Ciba Specialty Chemicals Product name: Darocur 1173, Irgacure 184], α-aminoacetophenones [for example, Ciba Specialty Chemicals Co., Ltd., product names: Irgacure 907, Irgacure 369], α-aminoacetophenones Examples thereof include combined use with thioxanthones (for example, isopropylthioxanthone, diethylthioxanthone), acylphosphine oxides [for example, trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.], and the like. Examples of the hydrogen abstraction type include a combined use of benzophenones and an amine, and a combined use of thioxanthone and an amine. Further, an intramolecular cleavage type and a hydrogen abstraction type may be used in combination. Of these, oligomerized α-hydroxyacetophenone and acrylated benzophenones are preferably used. More specifically, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] [for example, Lambertiti S.P.A, trade name: ESACURE KIP150], acrylic Examples thereof include benzophenone [for example, trade name: Ebecryl P136, manufactured by Daicel UCB Co., Ltd.], imide acrylate, and the like.

  As the crosslinking agent used as the component (F), an organic peroxide is preferably used. Specifically, for example, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane; 2,5-dimethyl-2,5-di (benzoylperoxy) -hexane; t -Butylperoxybenzoate; Dicumyl peroxide; t-Butylcumyl peroxide; Diisopropylbenzohydroperoxide; 1,3-bis- (t-butylperoxyisopropyl) -benzene; Benzoyl peroxide; 1,1-di And (t-butylperoxy) -3,3,5-trimethylcyclohexane.

  As said monomer used as (F) component, a (meth) acrylic acid ester monomer is preferable. The molecular weight of the monomer is preferably less than 1,000, and more preferably 150 to 600. (Meth) acrylic acid ester monomers include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol monoethyl ether ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) Acrylate, isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (Meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meta ) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol acrylate, etc.

  Among the (meth) acrylic acid ester monomers, those having a glass transition temperature (Tg) of 50 ° C. or higher are preferably used. When the glass transition temperature is 50 ° C. or higher, sufficient low moisture permeability can be obtained, the surface tackiness of the cured product can be reduced, and stickiness can be suppressed. On the other hand, the upper limit of the glass transition temperature is not particularly limited, but if the glass transition temperature is too high, the hardness of the cured product becomes too high depending on the amount of (meth) acrylic acid ester monomer added. Since it may not be preferable as it is, it is preferable that it is 150 degrees C or less. From the balance of low moisture permeability, stickiness and adhesion, the glass transition temperature is more preferably in the range of 80 to 130 ° C.

  Moreover, it is preferable that the alcohol residue of the said (meth) acrylic acid ester monomer is a hydrocarbon group which has a C5-C16 cyclic structure. If it is a hydrocarbon group having a cyclic structure having 5 or more carbon atoms, it is considered that low moisture permeability can be obtained from its bulkiness. On the other hand, if it is 16 or less, the above-mentioned preferable glass transition temperature is obtained. And can have a suitable hardness, and a balance between stickiness and adhesion can be obtained. From the above viewpoint, the alcohol residue of the (meth) acrylic acid ester monomer is preferably a hydrocarbon group having a cyclic structure having 8 to 12 carbon atoms. In particular, those in which the alcohol residue is a bridged cyclic hydrocarbon group are preferred, and specifically, those having a bicyclic alicyclic hydrocarbon group such as isobornyl (meth) acrylate, dicyclopentanyl (meta ) Those having a tricyclic alicyclic hydrocarbon group such as acrylate and dicyclopentenyl (meth) acrylate are preferred. Furthermore, saturated bridged cyclic hydrocarbon groups are preferred, and more specifically, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate are particularly preferred.

  The said (meth) acrylic acid ester monomer may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the range of 1-70 mass parts is preferable with respect to 100 mass parts of said (D) component, and, as for the compounding quantity of a (meth) acrylic acid ester monomer, More preferably, it is the range of 10-50 mass parts. By setting the content of the (meth) acrylic acid ester monomer content to 1 part by mass or more, particularly 10 parts by mass or more, the effect of adding the monomer, that is, low moisture permeability, suppression of stickiness, and adherend Adhesiveness is sufficiently obtained, and by setting it to 70 parts by mass or less, particularly 50 parts by mass or less, there is no problem that the hardness is too high.

  The ultraviolet curable resin composition (2) can be mixed with a thixotropic agent as required. By using this thixotropic agent in combination with the specific urethane oligomer of the component (D), the thixotropy can be effectively improved and the molding processability can be improved. As this thixotropic agent, both inorganic fillers and organic thickeners can be used.

  Examples of the inorganic filler include surface-treated fine silica of wet silica and dry silica, and natural minerals such as organic bentonite. Specifically, fine silica powder pulverized by a dry method [for example, product name: Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.], fine powder obtained by modifying this fine silica powder with trimethyldisilazane [for example, Nippon Aerosil Product name: Aerosil RX300, etc.] and fine powder obtained by modifying the above silica fine powder with polydimethylsiloxane [for example, product name: Aerosil RY300, manufactured by Nippon Aerosil Co., Ltd.]. The average particle diameter of the inorganic filler is preferably 5 to 50 μm and more preferably 5 to 12 μm from the viewpoint of thickening.

  Examples of the organic thickener include amide wax, hydrogenated castor oil, and mixtures thereof. Specifically, hydrogenated castor oil, which is a hydrogenated product of castor oil (non-drying oil whose main component is ricinoleic acid) [for example, manufactured by Zude Chemie Catalysts Co., Ltd., trade name: ADVITOLL 100, manufactured by Enomoto Kasei Co., Ltd., product Name: Disparon 305 etc.] and high-grade amide wax which is a compound obtained by substituting hydrogen of ammonia with an acyl group [for example, trade name: Disparon 6500, manufactured by Enomoto Kasei Co., Ltd.].

  Among these thixotropic agents, organic thickeners are particularly preferable. Natural mineral-based inorganic fillers cannot avoid impurities such as heavy metals, and surface-treated fine silica may change the wettability of the surface and change the viscosity of the composition, and depending on the type of surface treatment agent May generate harmful gas to the equipment during use. Further, among organic thickeners, amide wax is particularly preferably hydrogenated castor oil because the presence of amine derived from the raw material may increase the crosslink density and increase the hardness.

  When this thixotropy imparting agent is blended, the blending amount is preferably 0.5 to 10 parts by mass, particularly 1 to 100 parts by mass with respect to 100 parts by mass of the unsaturated group-containing urethane oligomer of the component (D). The range of 5 parts by mass is more preferable.

[UV curable resin composition (3)]
Next, the ultraviolet curable resin composition (3) will be described.
The ultraviolet curable resin composition (3) is as described above.
(G) a hydrogenated conjugated diene-aromatic vinyl copolymer (H) (meth) acrylate monomer containing a photocurable functional group, and
(I) An ultraviolet curable resin composition containing an aminoacetophenone photopolymerization initiator.

  Among the monomers constituting the hydrogenated conjugated diene-aromatic vinyl copolymer containing the photocurable functional group (G), examples of the conjugated diene monomer include 1,3-butadiene and isoprene. 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. Among these, 1,3-butadiene and / or isoprene are preferable from the viewpoint of securing rubber elasticity after curing, and 1,3-butadiene is particularly preferable. These may be used alone or in combination of two or more.

  Among the monomers constituting the hydrogenated conjugated diene-aromatic vinyl copolymer, the aromatic vinyl monomer includes styrene, α-methyl styrene or paramethyl styrene after rubber is cured. Of these, styrene is particularly preferable. These may be used alone or in combination of two or more.

  Further, the photocurable functional group contained in the hydrogenated conjugated diene-aromatic vinyl copolymer of the component (G) is preferably a photocurable unsaturated hydrocarbon group, and the photocurable unsaturated hydrocarbon group. It is particularly preferred that the group is a (meth) acryloyl group.

The hydrogenated conjugated diene-aromatic vinyl copolymer containing the photocurable functional group of the component (G) is not particularly limited, but is preferably produced as follows.
(A) In a saturated hydrocarbon solvent, a conjugated diene monomer and an aromatic vinyl monomer are polymerized with a dilithium initiator to obtain a weight average molecular weight of 5,000 to 40,000 and a molecular weight distribution of 3.0 or less. Producing a conjugated diene-aromatic vinyl copolymer having:
(B) reacting the conjugated diene-aromatic vinyl copolymer and alkylene oxide to produce a conjugated diene-aromatic vinyl copolymer polyol;
(C) hydrogenating the conjugated diene-aromatic vinyl copolymer polyol to produce a hydrogenated conjugated diene-aromatic vinyl copolymer polyol;
(D) a method for producing a photocurable liquid resin, comprising the step of reacting the hydrogenated conjugated diene-aromatic vinyl copolymer polyol with a photocurable unsaturated hydrocarbon group-containing compound. .

  First, as a first step (A), a conjugated diene-aromatic vinyl copolymer (a conjugated diene-aromatic vinyl copolymer ( Hereinafter, “sometimes referred to as a copolymer according to component (G)” is produced. Since the main polymerization is living anionic polymerization, the polymerization can be performed while controlling the molecular weight and molecular weight distribution. The molecular weight can be obtained by polymerizing a polymer having a predetermined molecular weight depending on the amount of the dilithium initiator and the above monomer. In particular, when the weight average molecular weight is 5,000 or more, a narrow polymer having a molecular weight distribution of 2 or less is used. Easy to get. If desired, anionic polymerization may be carried out in the presence of a randomizer.

  Next, as the second step (b), the copolymer according to the present invention is conjugated diene having hydroxyl groups at both ends by an equivalent reaction between the copolymer end which is a living anion and alkylene oxide. An aromatic vinyl copolymer polyol (hereinafter sometimes referred to as “copolymer polyol according to component (G)”) can be obtained.

  Furthermore, as a third step (c), the copolymer polyol according to the present invention having a double bond in the main chain is subjected to a hydrogenation reaction (hereinafter referred to as a hydrogenation reaction), whereby the main chain is unsaturated. Hydrogenated conjugated diene-aromatic vinyl copolymer polyol (hereinafter referred to as "hydrogenated copolymer polyol according to component (G)") having no heavy bond or having a few unsaturated double bonds in the main chain. ) Can be obtained.

  And as a 4th step (d), photocurable unsaturated hydrocarbon group containing compound is made to react with the hydrogenated copolymer polyol which concerns on the (G) component obtained as mentioned above, and photocurable. A hydrogenated conjugated diene-aromatic vinyl copolymer containing a functional group is obtained.

  The dilithium initiator is not particularly limited, and known ones can be used. For example, Japanese Patent Publication No. 1-53681 discloses a method for producing a dilithium initiator by reacting a monolithium compound with a disubstituted vinyl or an alkenyl group-containing aromatic hydrocarbon in the presence of a tertiary amine. ing.

  Monolithium compounds used when producing a dilithium initiator include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, tert-octyl lithium, and n-decyl. Examples thereof include lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, and among these, sec-butyl lithium is preferable.

  Examples of the tertiary amine used when producing the dilithium initiator include lower aliphatic amines such as trimethylamine and triethylamine, N, N-diphenylmethylamine, and the like, and triethylamine is particularly preferable. Examples of the disubstituted vinyl or alkenyl group-containing aromatic hydrocarbon include 1,3- (diisopropenyl) benzene, 1,4- (diisopropenyl) benzene, 1,3-bis (1-ethylethenyl). ) Benzene, 1,4-bis (1-ethylethenyl) benzene and the like are preferred.

  The solvent used in the preparation of the dilithium initiator and the production of the copolymer may be an organic solvent inert to the reaction, and is a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound. For example, n-butane, l-butane, n-pentane, l-pentane, cis-2-butene, trans-2-butene, l-butene, n-hexane, n-heptane, n-octane, One or two kinds selected from l-octane, methylcyclopentane, cyclopentane, cyclohexane, 1-hexene, 2-hexene, 1-pentene, 2-pentene, benzene, toluene, xylene, ethylbenzene and the like are used. Of these, n-hexane and cyclohexane are usually used.

  Further, examples of the alkylene oxide used in the polyolization reaction that reacts with the terminal which is the living anion of the copolymer according to the present invention to generate a hydroxyl group at both terminals include ethylene oxide, propylene oxide, butylene oxide, and the like. . This polyol reaction is preferably performed immediately after the polymerization reaction.

  If the weight average molecular weight of the copolymer polyol according to the component (G) obtained by the polyol reaction is 5,000 or more, the molecular weight between crosslinking points can be increased, and the elastic modulus is lowered after the photocuring reaction. In addition, it is preferable as a rubbery material because it can be stretched large. On the other hand, if the weight average molecular weight is 40,000 or less, the polymerization viscosity does not become too high when polymerization is performed with a dilithium catalyst, and the solid content concentration is lowered as a polymerization process. This is preferable because it is not necessary. Moreover, various influences by a low molecular weight component and a high molecular weight component can be suppressed as molecular weight distribution is 3.0 or less. In particular, since the viscosity is greatly affected by the molecular weight, slight fluctuations in the molecular weight cause viscosity variations. Since a copolymer having a molecular weight distribution can be synthesized in this way, a copolymer having the same molecular weight can be obtained with good reproducibility, and an effect of stabilizing the viscosity can be expected. With such a liquid material, the dispenser can be satisfactorily applied when the grip layer 2 is formed. In this case, the variation in the viscosity of the material causes a variation in the dimensions after the application. Stabilization is important, and the molecular weight distribution is preferably 3.0 or less.

The hydrogenation reaction for obtaining the hydrogenated copolymer polyol according to the component (G) is carried out by hydrogenating the copolymer polyol according to the component (G) in the presence of a hydrogenation catalyst in an organic solvent under hydrogen pressure. Done. The hydrogenation catalyst used in this hydrogenation reaction is a heterogeneous catalyst such as palladium-carbon, reduced nickel, rhodium, or the like, or an organic nickel compound such as nickel naphthenate or nickel octoate, or cobalt naphthenate or cobalt octoate. A homogeneous catalyst in which an organocobalt compound and an organoaluminum compound such as triethylaluminum and triisobutylaluminum or an organolithium compound such as n-butyllithium and sec-butyllithium are combined can be used. As a cocatalyst, an ether compound such as tetrahydrofuran, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether may be used. In addition, as another hydrogenation reaction method, for example, the copolymer according to the component (G) before hydrogenation is mixed with dicyclopentadienyl titanium halide, organic carboxylate nickel, organic carboxylate nickel and the periodic table. Hydrogenation catalysts composed of Group I to III organometallic compounds, catalysts for nickel, platinum, barium, ruthenium, rhenium, rhodium metal catalysts, cobalt, nickel, rhodium, ruthenium complexes, etc. supported on carbon, silica, diatomaceous earth, etc. In the presence of hydrogen pressurized to about 0.1 to 10 MPa, or in the presence of lithium aluminum hydride, p-toluenesulfonyl hydrazide, Zr—Ti—Fe—V—Cr alloy, Zr—Ti—Nb—Fe— the presence of V-Cr alloy, a hydrogen storage alloy such as LaNi ₅ alloy or 0.1~10MPa about A method of hydrogenating under pressurized hydrogen, and a di-p-tolyl-bis (1-cyclopentadienyl) titanium / cyclohexane solution and an n-butyllithium / n-hexane solution were mixed under hydrogen. Examples of the method include hydrogenation under hydrogen pressurized to about 0.1 to 10 MPa using the hydrogenation catalyst obtained.

  Among the various hydrogenation catalysts described above, a Ziegler hydrogenation catalyst or a palladium-carbon hydrogenation catalyst comprising a combination of a transition metal compound and an alkylaluminum compound is preferred. Such transition metal compounds include tris (acetylacetonato) cobalt, bis (acetylacetonato) nickel, tris (acetylacetonato) iron, tris (acetylacetonato) chromium, tris (acetylacetonato) manganese, bis (acetyl). Acetonato) manganese, tris (acetylacetonato) ruthenium, bis (acetylacetonato) cobalt, bis (cyclopentadienyl) dichlorotitanium, bis (cyclopentadienyl) dichlorozirconium, bis (triphenylphosphine) cobalt dichloride, Examples thereof include bis (2-hexanoate) nickel, bis (2-hexanoate) cobalt, titanium tetraisopropoxide, and titanium tetraethoxide. Among these, bis (acetylacetonato) nickel and tris (acetylacetonato) cobalt are preferable from the viewpoint of high hydrogenation activity.

  Alkyl aluminum compounds used for Ziegler hydrogenation catalysts include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, methylaluminum. Examples include dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum sesquichloride and the like. Among these, triisobutylaluminum, triethylaluminum, and diisobutylaluminum hydride are preferable from the viewpoint of hydrogenation activity, and triisobutylaluminum is most preferable.

  Although there is no particular limitation on the use form of the Ziegler-type hydrogenation catalyst in the hydrogenation reaction, a method in which a catalyst solution in which a transition metal compound and an alkylaluminum compound are reacted in advance is prepared and added to the polymerization solution is preferably cited. I can do it. The amount of the alkylaluminum compound used in this case is preferably 0.2 to 5 mol with respect to 1 mol of the transition metal compound. The catalyst preparation reaction is carried out in a temperature range of about -40 to 100 ° C, preferably 0 to 80 ° C, and the reaction time is usually in the range of 1 minute to 3 hours.

  The hydrogenation reaction is usually performed at a temperature of 50 to 180 ° C., preferably 70 to 150 ° C., and at a hydrogen pressure of about 0.5 to 10 MPa, preferably 1 to 5 MPa. When the hydrogenation temperature is lower than 50 ° C., and when the hydrogen pressure is lower than 0.5 MPa, the catalytic activity is lowered, which is not preferable. Therefore, it is not preferable. In general, a Ziegler-type hydrogenation catalyst is a catalyst having a very high hydrogenation activity, and it is not preferable to set the hydrogen pressure higher than 10 MPa because it is not necessary and increases the burden on the apparatus.

  In order to introduce a photocurable functional group into the terminal of the hydrogenated copolymer polyol according to the component (G), a photocurable functional group-containing compound, preferably a photocured, is added to the hydrogenated copolymer polyol. An unsaturated hydrocarbon group-containing compound, particularly preferably a (meth) acryloyl group-containing compound is reacted. Here, as the (meth) acryloyl group-containing compound, acryloyloxyalkyl isocyanate and methacryloyloxyalkyl isocyanate are preferable, and the hydrogenated copolymer polyol is (meth) acrylated by reaction with these. Examples of the acryloyloxyalkyl isocyanate include 2-acryloyloxyethyl isocyanate, and examples of the methacryloyloxyalkyl isocyanate include 2-methacryloyloxyethyl isocyanate.

  Next, the (meth) acrylate monomer of the component (H) not only reduces the viscosity of the composition (3) before curing, but also improves various physical properties after curing. That is, it is possible to improve adhesive strength and low moisture permeability, adjust hardness and tackiness, and improve Eb (elongation) and Tb (breaking strength). The molecular weight of the (meth) acrylate monomer is preferably less than 1,000, and more preferably 150 to 600.

  Specific examples of the (meth) acrylate monomer include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, diethylene glycol monoethyl ether ( (Meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylol dicyclopentane (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate , Isoamyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl (meth) acrylate, isodecyl (meth) acrylate, iso Cutyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauroxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripyrene glycol (meta ) Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol acrylate and the like. Among these, isobornyl acrylate, dicyclopentanyl acrylate and dicyclopentenyl acrylate are particularly preferably used.

  When the blending amount of the (H) component (meth) acrylate monomer is 100 parts by mass in combination with the above (G) component, the ratio of (part (G) component / (H) component) is (20 / 80) to (100/0) is preferable, and (30/70) to (90/10) is more preferable. By setting the (H) component (meth) acrylate monomer to 10 parts by mass or more, the viscosity of the ultraviolet curable resin composition (3) can be appropriately reduced, and good moldability can be achieved. The workability at the time of forming the grip layer 2 with the ultraviolet curable resin composition (3) on the base film 1 can be effectively improved. Moreover, by setting the blending ratio to 70 parts by mass or less, the viscosity of the composition does not become too low, and the ultraviolet curable resin composition (3) immediately after formation becomes difficult to flow down. Furthermore, the adhesive strength and elasticity of the cured composition (grip layer 2) are also good.

  Next, as the aminoacetophenone photopolymerization initiator of the component (I), for example, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [Ciba Specialty Chemicals] Product name: Irgacure 907], 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone [Ciba Specialty Chemicals Co., Ltd., product name: Irgacure 369] 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -1-butanone [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 379], etc. Is mentioned.

  The aminoacetophenone-based photopolymerization initiator has high reaction activity, and is less susceptible to oxygen inhibition on the surface of the ultraviolet curable resin composition (3) due to the presence of nitrogen atoms, so that the curability of the ultraviolet curable resin composition (3) is increased. At the same time, the adhesiveness (tackiness) after curing can be reduced and the compression set can be reduced. Thereby, the ultraviolet curable resin composition (3) exhibits good performance as the grip layer 2.

  The amount of the photopolymerization initiator of the component (I) is preferably 0.1 to 6 parts by mass, more preferably 0.5 to 100 parts by mass in total of the component (G) and the component (H). -5 parts by mass, more preferably 1-4 parts by mass.

  In the ultraviolet curable resin composition (3), the aminoacetophenone photopolymerization initiator (I) may be used in combination with another photopolymerization initiator as desired. Other photopolymerization initiators include benzoin derivatives and benzyl ketals [for example, Ciba Specialty Chemicals, trade name: Irgacure 651], α-hydroxyacetophenones [for example, Ciba Specialty Chemicals, Inc., trade names: Darocur 1173, Irgacure 184, Irgacure 127, Irgacure 2959], acylphosphine oxides [for example, Ciba Specialty Chemicals, Inc., trade names: Irgacure 819, Irgacure TPO] and the like, and examples of the hydrogen abstraction type include a combination of benzophenones and amine, a combination of thioxanthone and amine, and the like.

  In addition, as oligomerized α-hydroxyacetophenone, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] [for example, Lamberti S. et al. p. A product, trade name: ESACURE KIP150, etc.], and acrylated benzophenones such as acrylated benzophenone [for example, trade name: Ebecryl P136, produced by Daicel UCB Co., Ltd.], imide acrylate, and the like.

  Furthermore, benzoyl methyl ether, benzoyl ethyl ether, benzoyl butyl ether, benzoyl isopropyl ether, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl ] Propanol oligomer, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer and 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropylthioxanthone, o-benzoyl Methyl benzoate and [4- (methylphenylthio) phenyl] phenylmethane can also be used in combination.

  In the ultraviolet curable resin composition (3), as in the case of the ultraviolet curable resin composition (1), if desired, an inorganic filler and / or an organic thickener may be blended as a thixotropic agent. Thereby, the adhesiveness (tackiness) of the composition can be further reduced. Examples of these inorganic fillers and organic thickeners are the same as those shown in the description of the ultraviolet curable resin composition (1), and the particle diameter of the inorganic filler may be in the same range. preferable.

  The blending amount of these thixotropic agents is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, with respect to 100 parts by mass in total of the component (G) and the component (H). More preferably, it is 1 to 5 parts by mass.

  In this ultraviolet curable resin composition (3), as in the case of the ultraviolet curable resin composition (1), terminal (meth) acrylate oligomers and stabilizers can be blended. As an oligomer and a stabilizer, the thing similar to what was illustrated by description of the said ultraviolet curing resin composition (1) can be mentioned.

  It is preferable that the compounding quantity of a terminal (meth) acrylate oligomer is 100 mass parts or less with respect to a total of 100 mass parts of the said (G) component and (H) component. Moreover, it is preferable that the compounding quantity of a stabilizer is 0.1-5 mass parts with respect to a total of 100 mass parts of (G) component and (H) component, More preferably, it is 0.5-3 mass parts. More preferably, it is 0.5 to 2 parts by mass.

  Further, in this ultraviolet curable resin composition (3), as in the case of the ultraviolet curable resin composition (1), a terpene resin, terpene phenol resin, coumarone resin, coumarone-indene resin, petroleum hydrocarbon, rosin Appropriate amounts of additives such as various tackifiers such as derivatives and colorants such as titanium black can be added.

  In the present invention, an ultraviolet curable resin such as the ultraviolet curable resin compositions (1) to (3) is applied to one side of the base film 1 and cured by ultraviolet irradiation to form the grip layer 2. In this case, the grip layer 2 may be entirely formed on one surface side of the base film 1 as shown in FIG. 1, but as shown in FIG. It is also possible to form the grip layer 2 in the form of dots, thereby reducing the amount of the ultraviolet curable resin used and reducing the material cost. Also, as shown in FIG. 3, an ultraviolet curable resin is applied to the shape of the final product (for example, a ring shape as shown in FIG. 3) and cured to form a grip layer 2 having the final shape on the base film 1. Thus, the material can be further reduced.

  The method of applying the ultraviolet curable resin on the base film 1 can be performed by any method, for example, gravure coating, roll coating, spin coating, reverse coating, bar coating, screen coating, blade coating, air knife coating, Methods such as dipping, dispensing, and ink jet can be used.

  The curing operation by ultraviolet irradiation can be performed by a known method using an ultraviolet source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a microwave excimer lamp. In this case, the atmosphere for irradiating ultraviolet rays is appropriately set according to the ultraviolet curable resin to be used, and can be, for example, an inert gas atmosphere such as nitrogen gas or carbon dioxide gas, or an atmosphere having a reduced oxygen concentration. A normal air atmosphere may be used. The irradiation atmosphere temperature is also appropriately set according to the ultraviolet curable resin, and can usually be 10 to 200 ° C. Further, the ultraviolet curable resin can be stabilized in its properties by irradiating active energy rays again after curing or by applying heat.

  The thickness of the grip layer 2 is appropriately set according to the shape, size, mechanism, etc. of the turntable or disk drive in which the disk stopper is used, but is usually 10 to 1,000 μm, particularly 50 to 500 μm. It is common to set the degree.

  Next, the pressure-sensitive adhesive layer 3 can be formed by applying a suitable pressure-sensitive adhesive to the other surface of the base film 1 with a suitable pressure-sensitive adhesive such as a silicone-based pressure-sensitive adhesive. It is preferable to stick the tape to form the adhesive layer 3. As this double-sided adhesive tape, a commercially available tape can be used. Specifically, Teraoka Manufacturing Co., Ltd. “No. 773”, “No. 777”, “No. 7783”; Sumitomo 3M Co., Ltd. “Y4914”, “Y4920”; Nitto Denko Corporation “TW-Y01”, “No. 5000N (C)”, “No. 5000 NS”, “No. 5015”; Sony Chemical & Information Device Corporation “G4000” ”,“ G9000 ”,“ G9900 ”; Sliontec“ 5686 ”; Sekisui Chemical Co., Ltd.“ 575 ”,“ 5754 ”,“ 5760LS (E) ”,“ 5782LSV ”; Tessatape“ 5197 ” DIC Corporation "8810TD", "8408TD" etc. can be illustrated.

  The disc stopper of the present invention is usually used by being attached to a turntable that rotates an optical recording disc such as a CD, DVD, or BD. It can be used by cutting into an appropriate shape according to the shape of the turntable, the drive mechanism, etc. For example, it can be used by punching into a ring shape of an appropriate size according to the turntable.

EXAMPLES Hereinafter, although an Example and a reference example are shown and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example.

[ Reference Example 1]
The following blending components were kneaded with a planetary mixer at the following ratio to obtain the ultraviolet curable resin composition (1). This was heated to 70 to 80 ° C., applied onto a PET film (base film) having a thickness of 100 μm using a knife coater, and cured by irradiation with ultraviolet rays to form a grip layer having a thickness of 400 μm. For the ultraviolet irradiation, a metal halide lamp was used, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 160 mW / cm ² (wavelength 320 to 390 nm) and an integrated light amount of about 9,000 mJ / cm ² .

(Compounding ingredients)
Hydrogenated polybutadiene polymer 1 15 parts by weight Hydrogenated polybutadiene polymer 2 35 parts by weight Hydrogenated polybutadiene urethane modified polymer 5 parts by weight Acrylic ester monomer 45 parts by weight Photoradical polymerization initiator 1 part by weight Inorganic filler 3.5 parts by weight Organic increase 3 parts by weight of adhesive 2 Note)
-Hydrogenated polybutadiene polymer 1: SPBDA-S manufactured by Osaka Organic Chemical Industry Co., Ltd. (weight average molecular weight: 6,000, f = 2 (f means a functional group (acryloyl group)))
Hydrogenated polybutadiene polymer 2: SPBA-S (weight average molecular weight: 7,000, f = 2) manufactured by Osaka Organic Chemical Industry Co., Ltd.
Hydrogenated polybutadiene urethane modified polymer: Osaka Organic Chemical Industry Co., Ltd. (weight average molecular weight: 17,000, f = 2, HDI modified)
・ Acrylic acid ester monomer: Osaka Organic Chemical Industry Co., Ltd., IBXA (isobonyl acrylate)
Photoradical polymerization initiator: Irgacure 369 (α-aminoacetophenone) manufactured by Ciba Specialty Chemicals
・ Inorganic filler: Nippon Aerosil Co., Ltd., AEROSIL200 (silica powder)
・ Organic thickener 2: ADVITOLOL 100 (mixture of hydrogenated castor oil and amide wax), manufactured by Zude Chemie Catalysts Co., Ltd.

  In addition, the same ultraviolet curable resin composition (1) was formed into a film and cured in the same manner to prepare a test piece (thickness 2 mm). According to JIS K6262, 100 ° C., 24 hours, compression rate 25% The compression set was measured under the following conditions. The result was 5% and the compression set was very small.

Next, a double-sided adhesive tape “G9900” manufactured by Sony Chemical & Information Device Co., Ltd. was attached to the other side of the base film to form an adhesive layer, which was used as a disk stopper. This was punched into a predetermined shape, attached to a turntable of an optical disk drive, a CD was brought into close contact with a predetermined pressure, and a rotational running test was performed by running under the following conditions. The CD was able to rotate stably without generating.
(Rotating test condition)
At an environmental temperature of 23 ° C. and a disk rotation speed of 10,000 rpm, rotation 1 minute-stop 10 seconds was repeated 100 times.

[ Reference Example 2]
The following blending components were kneaded with a planetary mixer at the following ratio to obtain the ultraviolet curable resin composition (1). This was heated to 90 to 100 ° C., applied onto a PET film (base film) having a thickness of 100 μm using a knife coater, and cured by irradiating with ultraviolet rays to form a grip layer having a thickness of 400 μm. For the ultraviolet irradiation, a metal halide lamp was used, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 160 mW / cm ² (wavelength 320 to 390 nm) and an integrated light amount of about 9,000 mJ / cm ² .

(Compounding ingredients)
Hydrogenated polybutadiene polymer 1 15 parts by weight Hydrogenated polybutadiene polymer 2 35 parts by weight Hydrogenated polybutadiene urethane modified polymer 5 parts by weight Acrylic ester monomer 45 parts by weight Photoradical polymerization initiator 1 part by weight Inorganic filler 3.5 parts by weight Organic increase 3 parts by weight of adhesive 1 Note)
Organic thickener 1: manufactured by Ito Oil Co., Ltd., ASA T1800 (Amide Wax)
Other components are the same as in Example 1.

Further, the same ultraviolet curable resin composition (1) was formed into a film and cured in the same manner to prepare a test piece (thickness 2 mm), and the compression set was measured in the same manner as in Reference Example 1. The result was 8%, and the compression set was very small.

Next, when the disk stopper to form the other side in the double-sided adhesive tape bonding the pressure-sensitive layer in the same manner as in Reference Example 1 of the substrate film was subjected to rotary traveling test in the same manner as in Reference Example 1, shift Ya The CD could be stably rotated without causing slip or rotation failure.

[Example 1 ]
400 g of a polyester diol compound (number average molecular weight 2,000) obtained from 2,4-diethyl-1,5-pentanediol and phthalic anhydride, 82.4 g of norbornane diisocyanate, di-t of the antioxidant -Butyl-hydroxyphenol 0.10g was put into the 1 liter four necked flask provided with the stirrer, the cooling tube, and the thermometer, and it was made to react at 80 degreeC for 2 hours. Then, 46.2 g of 2-hydroxyethyl acrylate, 0.10 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of titanium tetra (2-ethyl-1-hexanolate) as an addition reaction catalyst were added, and the mixture was heated at 85 ° C. for 6 hours. Reacted. A part of the reaction solution was taken out and the absorption peak of 2,280 cm ⁻¹ isocyanate group disappeared in the infrared absorption spectrum, whereby the end point of the reaction was confirmed, and a urethane oligomer used as component (A) was obtained. It was 18,000 when the number average molecular weight was calculated | required by the polystyrene conversion value about the obtained urethane oligomer using the gel permeation chromatography.

The obtained urethane oligomer and each of the following components were kneaded at 70 ° C. using a planetary mixer to obtain the ultraviolet curable resin composition (2). This is coated on a PET film (base film) having a thickness of 100 μm using a knife coater, cured by irradiating with ultraviolet rays to form a grip layer having a thickness of 400 μm, and further at 120 ° C. for 4 hours in an air atmosphere. Baking process. For the ultraviolet irradiation, a metal halide lamp was used, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 130 mW / cm ² and an integrated light amount of about 8,000 mJ / cm ² .

(Compounding ingredients)
Urethane oligomer 100 parts by mass Carbodiimide compound 2 parts by mass Phenoxyethyl acrylate 25 parts by mass Note)
-Carbodiimide compound: Liquid carbodiimide compound Nisshinbo Co., Ltd. product name [Elastost ab H01]
・ Phenoxyethyl acrylate: “Light acrylate PO-A” manufactured by Kyoei Chemical Co., Ltd.

Further, the same ultraviolet curable resin composition (2) Similarly to ultraviolet curing a film of, create baked to specimen (thickness 0.6 mm), the compression set in the same manner as in Reference Example 1 It was measured. The result was 6%, and the compression set was very small.

Next, when the disk stopper to form the other side in the double-sided adhesive tape bonding the pressure-sensitive layer in the same manner as in Reference Example 1 of the substrate film was subjected to rotary traveling test in the same manner as in Reference Example 1, shift Ya The CD could be stably rotated without causing slip or rotation failure.

[ Reference Example 3 ]
After adding 1 mol of 1,3- (diisopropenyl) benzene to a fully dehydrated and purified cyclohexane solvent, 2 mol of triethylamine and 2 mol of sec-butyllithium are sequentially added and stirred at 50 ° C. for 2 hours. A dilithium polymerization initiator was prepared. In a 7 liter polymerization reactor purged with argon, 1.90 kg of dehydrated and purified cyclohexane, 2.00 kg of a hexane solution of 22.9% by mass of 1,3-butadiene monomer, and a cyclohexane solution of 20.0% by mass of styrene monomer were added. After adding 130.4 ml of a hexane solution of 0.765 kg, 1.6 mol / liter of 2,2-di (tetrahydrofuryl) propane, 108.0 ml of a 0.5 mol / liter dilithium polymerization initiator was added. Polymerization was started. Polymerization was carried out for 1.5 hours while raising the temperature of the polymerization reactor to 50 ° C., then 108.0 ml of a 1 mol / liter ethylene oxide cyclohexane solution was added, and the mixture was further stirred for 2 hours, and then 50 ml of isopropyl alcohol was added. did. A hexane solution of the copolymer was precipitated in isopropyl alcohol and sufficiently dried to obtain a copolymer polyol. This copolymer polyol was a OH group styrene-butadiene copolymer at both terminals, the styrene content was 25% by mass, the weight average molecular weight was 14,500, and the molecular weight distribution was 1.20.

  Next, 120 g of copolymer polyol was dissolved in 1 liter of hexane that had been sufficiently dehydrated and purified, and then nickel naphthenate, triethylaluminum, and butadiene prepared in separate containers in a 1: 3: 3 (molar ratio) ratio. The catalyst solution was charged so that the amount of nickel was 1 mol with respect to 1,000 mol of the butadiene portion in the copolymer solution. Hydrogen was added under pressure to 27,580 hPa (400 psi) in a sealed reaction vessel, and a hydrogenation reaction was performed at 110 ° C. for 4 hours. Thereafter, the catalyst residue was extracted and separated with hydrochloric acid having a concentration of 3 mol / L, and further centrifuged to separate and separate the catalyst residue. Thereafter, the hydrogenated copolymer polyol was precipitated in isopropyl alcohol and further sufficiently dried.

  100 g of a fully dried hydrogenated copolymer polyol was dissolved in cyclohexane, and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK: Karenz AOI) was slowly added dropwise with stirring at 40 ° C. Thereafter, the mixture was further stirred for 4 hours, precipitated in isopropyl alcohol and dried. The amount of 2-acryloyloxyethyl isocyanate added was 2.49 g. As described above, an acryloyl group-containing hydrogenated styrene-butadiene copolymer, which is a photocurable liquid resin, was obtained from the hydrogenated polymer polyol.

The obtained acryloyl group-containing hydrogenated styrene-butadiene copolymer and the following components were kneaded at 70 ° C. using a planetary mixer to obtain the ultraviolet curable resin composition (3). This was applied onto a PET film (base film) having a thickness of 100 μm using a knife coater and cured by irradiation with ultraviolet rays to form a grip layer having a thickness of 400 μm. For the ultraviolet irradiation, a metal halide lamp was used, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 160 mW / cm ² (wavelength 320 to 390 nm) and an integrated light amount of about 9,000 mJ / cm ² .

Acrylyl group-containing hydrogenated styrene-butadiene copolymer 70 parts by weight Acrylate monomer A 30 parts by weight Thixotropic agent 3 parts by weight Photopolymerization initiator A 1 part by weight Note)
Acrylate monomer A: Isobornyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: IBXA
・ Thixotropic agent: Hydrated castor oil, manufactured by Rockwood Additives Co., Ltd., trade name: ADVITROL100
Photopolymerization initiator A: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 369

Further, the same ultraviolet curable resin composition (3) was formed into a film and cured in the same manner to prepare a test piece (thickness 2 mm), and the compression set was measured in the same manner as in Reference Example 1. The result was 12% and the compression set was small.

Next, when the disk stopper to form the other side in the double-sided adhesive tape bonding the pressure-sensitive layer in the same manner as in Reference Example 1 of the substrate film was subjected to rotary traveling test in the same manner as in Reference Example 1, shift Ya The CD could be stably rotated without causing slip or rotation failure.

[ Reference Example 4 ]
The same acryloyl group-containing hydrogenated styrene-butadiene copolymer as used in Reference Example 3 and the following components were kneaded at 70 ° C. using a planetary mixer, and the ultraviolet curable resin composition (3 ) This was applied onto a PET film (base film) having a thickness of 100 μm using a knife coater and cured by irradiation with ultraviolet rays to form a grip layer having a thickness of 400 μm. For the ultraviolet irradiation, a metal halide lamp was used, and irradiation was performed in an air atmosphere under conditions of an illuminance of about 160 mW / cm ² (wavelength 320 to 390 nm) and an integrated light amount of about 9,000 mJ / cm ² .

Acrylyl group-containing hydrogenated styrene-butadiene copolymer 70 parts by mass Acrylate monomer A 30 parts by mass Thixotropic agent 3 parts by mass Photopolymerization initiator B 1 part by mass Note)
Photopolymerization initiator B: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals, Inc., trade name: Irgacure 907
-Others are the same as Example 4

Further, the same ultraviolet curable resin composition (3) was formed into a film and cured in the same manner to prepare a test piece (thickness 2 mm), and the compression set was measured in the same manner as in Reference Example 1. The result was 15% and the compression set was small.

Next, when the disk stopper to form the other side in the double-sided adhesive tape bonding the pressure-sensitive layer in the same manner as in Reference Example 1 of the substrate film was subjected to rotary traveling test in the same manner as in Reference Example 1, shift Ya The CD could be stably rotated without causing slip or rotation failure.

1 Base film 2 Grip layer 3 Adhesive layer

Claims (10)

A grip layer having a high static friction property is formed on one side of a base film made of a hard resin film, and an adhesive layer is formed on the other side. The disc is affixed to the turntable and placed on the turntable. a disk stopper to prevent the deviation, the above-mentioned grip layer,
(D) 100 parts by mass of an unsaturated group-containing ester urethane oligomer,
(E) 0.01 to 10 parts by mass of a compound containing at least one carbodiimide group in the molecule, and
(F) At least one of a photopolymerization initiator, a crosslinking agent, and a monomer
A disk stopper formed of an ultraviolet curable resin composition containing The unsaturated group-containing ester urethane oligomer of the component (D) is represented by the following general formula (1):

[Wherein R ¹ is a dehydroxylated residue of a monool compound containing at least one of a unsaturated group of (meth) acryloyl group and vinyl group, and R ² is a residue of a deisocyanate of an organic diisocyanate compound. Group R ³ is a dehydroxylated residue of a polyester diol compound having a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ and containing a cyclic group or a branched group, and A is a dehydrogenated residue of a diamine compound or Each of dehydrogenated residues p and r of the diol compound is 0 to 7, q is 0 to 3, provided that 1 ≦ p + r ≦ 10 when q = 0. ]
The disk stopper according to claim 1, which is an unsaturated group-containing urethane oligomer having a number average molecular weight of 5 × 10 ^{3 to} 5 × 10 ⁴ . The unsaturated group-containing urethane oligomer of the above component (D) (provided that q = 0 in the general formula ( 1 )) is subjected to a polyaddition reaction between the polyester diol compound and the organic diisocyanate compound. 3. The disk stopper according to claim 2 , wherein the disc stopper is obtained by forming an adduct having groups at both ends and then adding the monool compound to the isocyanate group. The unsaturated group-containing urethane oligomer of the component (D) (provided that q ≠ 0 in the general formula ( 1 )) is subjected to a polyaddition reaction between the polyester diol compound and the organic diisocyanate compound. Are formed at both ends, and then each of the diamine compound or each of the ends of the diol compound is added to an isocyanate group at one end of the adduct, and is added to an isocyanate group at the other end of the adduct. The disk stopper according to claim 2, which is obtained by adding the monool compound. The disk stopper according to any one of claims 1 to 4 , wherein the compound (E) containing a carbodiimide group is a liquid polycarbodiimide compound having a viscosity of 0.1 to 100 Pa · s. (F) above phenoxyethyl acrylate as a monomer component, a photopolymerization initiator 4- (2-hydroxyethoxy) phenyl - any one of claims 1 to 5 containing (2-hydroxy-2-propyl) ketone Disc stopper described in 1. The disk stopper according to any one of claims 1 to 6, wherein the hard resin film forming the base film is a polyethylene terephthalate (PET) film, a polypropylene (PP) film, or a polyethylene (PE) film. The disk stopper according to any one of claims 1 to 7, wherein the adhesive layer is an acrylic double-sided adhesive tape. The disk stopper according to any one of claims 1 to 8, wherein the grip layer is formed by applying the ultraviolet curable resin in a predetermined shape on a base film and irradiating with ultraviolet rays. The said grip layer is many dot-shaped grip layers which apply | coated the said ultraviolet curing resin in the shape of a dot on the base film, and were hardened | cured by irradiating with an ultraviolet-ray, The any one of Claims 1-9. Disc stopper.

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