JP2883954B2 - Active energy ray curable substance - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an active energy ray-curable substance.

Conventional technology and its problems Conventional polymers blended as a resin component in inks, paints, adhesives, pressure-sensitive adhesives, etc. include acrylic-based polymers that have been polymerized in organic solvents such as toluene, xylene, and ethyl acetate. Materials, so-called solvent type, are mainly used. However, in the case of a solvent-type polymer, it is necessary to volatilize the solvent at the time of its use, and various problems such as fire danger and pollution are caused.

In order to solve these drawbacks, high solid differentiation of the polymer has been studied. However, if the polymer is highly solid differentiated, the viscosity becomes high and workability and coatability cannot be avoided.

From this point of view, as a new alternative to the above method, a method in which the viscosity is reduced by dissolving in a reactive diluent curable by active energy rays or a method in which a substance curable by active energy rays is dissolved in a reactive diluent is applied. After the process, a method of forming a cured film by irradiating with active energy rays to form a cured film has been studied. However, even in this method, problems such as volatilization of the diluent due to irradiation and odor due to unreacted substances are caused. Further, the film formed by this method is insufficient in performance required as a film such as an ink, a paint, an adhesive, a pressure-sensitive adhesive and the like, particularly in terms of low-temperature flexibility and heat resistance.

Means for Solving the Problems In view of this situation, the present inventor has found that the coating film contains essentially no solvent and reactive diluent and has excellent film performance (particularly low-temperature flexibility and heat resistance) by irradiation with active energy rays. As a result of intensive studies to develop a novel active energy ray-curable substance capable of forming a cured film having the following properties, the present invention was finally completed.

That is, the present invention relates to (A) a divalent carbon having at least one reactive silicon group in a molecule and having a main chain of substantially -RO- (R is a carbon atom having 1 to 8 carbon atoms). An alkylene oxide polymer having a weight average molecular weight of about 1,000 to about 50,000, and (B) having a group capable of reacting with the reactive silicon group and a double bond in the molecule. The present invention relates to an active energy ray-curable substance obtained by subjecting an organic compound to a condensation reaction at room temperature or under heating.

In the present specification, the weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

The reactive silicon group in the alkylene oxide-based polymer used as the component (A) in the present invention refers to a hydrolysis which is hydrolyzed by a hydroxyl group or water capable of performing a silanol condensation reaction in the presence or absence of a silanol condensation catalyst. Means a group in which a reactive group is bonded to a silicon atom. [Wherein, R ¹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms selected from an alkyl group and an aryl group, X is a hydroxyl group or a hydrolyzable group, a is an integer of 0 or 1 to 3, b is 0 , 1 or 2,
n represents 0 or an integer of 1 to 19, respectively. However, 1 ≦ a +
It is assumed that b ≦ 4 is satisfied. ] The group represented by these can be mentioned.

In the above general formula, examples of the alkyl group represented by R ¹ include a methyl group, an ethyl group, an n-propyl group, and an n-
Examples include a butyl group, a tert-butyl group, an n-octyl group and the like, and examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group. Examples of the hydrolyzable group represented by X include a hydride group, a halogen group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an acyloxy group, a mercapto group, and the like.

The reactive silicon group may be present in the main chain of the alkylene oxide polymer or may be present at the terminal.

The divalent hydrocarbon group having 1 to 8 carbon atoms represented by R, for example, _{-CH 2 -, - (CH 2} ) 2 -, - (CH 2) 3 -, -CH (CH 3) CH _{2 -, -CH (C 2 H} 5) CH 2 -, -C (CH 3) 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 5, -
(CH ₂ ) _6- and the like.

The weight average molecular weight of the component (A) used in the present invention is:
It ranges from about 1000 to about 50,000.

As the organic compound as the component (B) used in the present invention, those generally used as a silane coupling agent can be widely used, and for example, Y- (R ² ) _m -SiZ ₃ (2) , Y is CH ₂ ＣC (CH ₃ ) COO— or CH ₂ CHCH—, R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, m is 0 or 1, or a hydroxyl group or a hydrolyzable group. Shown respectively. Where Y is CH ₂
When = CH- is indicated, m indicates 0. ] The compound represented by these can be mentioned.

Here, examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ² include —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, and —CH (CH ₃ ). _{CH 2 -, -CH (C 2} H 5) CH 2 -, -C (CH 3) 2 CH 2 -, - (CH 2) 4 -, - (CH 2) 5, -
(CH ₂ ) _6- and the like. Examples of the hydrolyzable group represented by Z include a hydride group, a halogen group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an acyloxy group, a mercapto group, and the like.

Specific examples of the compound represented by the general formula (2) include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and vinyltris (β-methoxyethoxy).
Silane, 2-styrylethyltrimethoxysilane, γ-
Examples thereof include methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane. These can be used alone or in combination of two or more.

The active energy ray-curable substance of the present invention is characterized in that (A)
The component (B) is manufactured by stirring and mixing the component (B) at room temperature or under heating and then subjecting it to a condensation reaction. During the condensation reaction, if necessary, a silanol condensation catalyst or water may be added to the reaction system.

The condensation reaction between the component (A) and the component (B) can be performed at room temperature or under heating. When the reaction is carried out under heating, the reaction temperature is not particularly limited, but usually it is desirable to be 150 ° C. or lower.

As the silanol catalyst to be used, conventionally known ones can be widely used, for example, titanates such as alkyl titanates and organosilicon titanates; tin octylate, dibutyltin laurate, dibutyltin maleate, dibutyltin phthalate and the like Metal salts of carboxylic acids; amine salts such as dibutylamine-2-ethylhexoate; and other acidic catalysts and basic catalysts. These may be used alone or in combination of two or more.

The above components (A) and (B) may have a hydrolyzable group in the molecule. In this case, hydrolysis occurs due to the presence of water or moisture in the air, and condensation occurs. The reaction proceeds easily.

The amount of the component (B) to be used is generally about 1 to 100 parts, preferably about 5 to 50 parts, more preferably 10 to 30 parts by weight, per 100 parts by weight of the component (A) (hereinafter simply referred to as "parts"). Parts. When a silanol condensation catalyst is added, the amount of addition is preferably about 0.1 to 10 parts, more preferably about 1 to 5 parts, per 100 parts of component (A). The water may be moisture in the air, but it is preferable to add water separately. In this case, the amount of water added is based on 100 parts of component (A).
About 0.1 to 10 parts is preferable, and about 1 to 5 parts is more preferable.

The active energy ray-curable substance obtained above has a repeating unit of -RO- (R is the same as above) in the main chain,
And it has a double bond in the molecule.

The active energy ray-curable substance obtained above can be easily cured by irradiation with active energy rays. As the active energy ray, conventionally known active energy rays can be widely exemplified, for example, visible light, light such as ultraviolet ray, α ray, β ray, γ
Radiation, such as radiation, X-rays, and electron beams.
UV rays include sunlight, low-pressure mercury lamps, high-pressure mercury lamps,
An ultra-high pressure mercury lamp, a xenon mercury lamp, a carbon arc lamp, a metal halide lamp and the like can be used.

When using light as an active energy ray, it is desirable to add a photosensitizer or a photopolymerization accelerator to the curable substance. As the photosensitizer and the photopolymerization accelerator, any conventionally known ones can be used. Examples of the photosensitizer include benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether,
Benzoins such as benzoin and 2-methylbenzoin;
9,10-anthraquinone, 1-chloroanthraquinone, 2
-Anthraquinones such as chloranthraquinone; benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, 4,4'-bis (diethylamino)
Benzophenones such as benzophenone and diethoxyacetophenone; sulfur compounds such as diphenyl disulfide tetramethylthiuram disulfide; methylene blue;
Eosin, fluorescein, 1-hydroxycyclohexyl phenyl ketone, benzyl methyl ketal and the like can be mentioned. In the present invention, such photosensitizers can be used alone or in combination of two or more. Further, as the photopolymerization accelerator, for example, diethyltriamine, tetraethylenepentamine, pentaethylenehexamine, N-methyldiethanolamine, aminoethylethanolamine, n-aminopiperazine, diaminodiphenylmethane, dimethylaniline, diethylaniline,
Examples thereof include amines such as dimethyltoluidine, diethyltoluidine, triethanolamine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and 2,4,6-dimethylaminomethylphenol. In the present invention, such a photopolymerization accelerator can be used alone or in combination of two or more.

The photosensitizer does not necessarily need to be used in combination with the photopolymerization accelerator, and can be used alone. The amount of the photosensitizer used is, per 100 parts of the active energy ray-curable substance,
Usually about 0.1 to 20 parts, preferably about 1 to 10 parts is good.
When a photopolymerization accelerator is used in combination, the amount of the photopolymerization accelerator is usually 0.1 parts per 100 parts of the active energy ray-curable substance.
About 10 parts, preferably about 0.1 to 5 parts.

The active energy ray-curable substance of the present invention can be added and blended as a resin component to various compositions such as inks, paints, adhesives and pressure-sensitive adhesives. In the present invention, the curable substance and a conventionally known active energy ray-curable substance such as a urethane acrylate or a functional acrylate can be used in combination.

The cured film of a composition such as an ink, a paint, an adhesive or a pressure-sensitive adhesive in which the active energy ray-curable substance of the present invention is blended,
Although it is excellent in low-temperature flexibility and heat resistance, these characteristics become remarkably excellent especially when it is blended in an adhesive.

When the active energy ray-curable substance of the present invention is blended with an adhesive, it is necessary to further blend a tackifier resin into the adhesive. As the tackifier resin, conventionally known resins can be widely used, for example, a resin having a polar group such as a rosin ester resin, a phenol resin, a xylene resin, a xylene phenol resin, a terpene phenol resin, an aromatic resin having a relatively small polarity, Examples include various petroleum resins such as aliphatic-aromatic copolymers and alicyclic resins, coumarone resins, low molecular weight polystyrene resins, and terpene resins. The amount of the tackifier resin is not particularly limited as long as it is 200 parts or less based on 100 parts of the active energy ray-curable resin. However, it is preferable to add about 10 to 150 parts. The tackifier resin can be directly mixed with the active energy ray-curable resin, but the tackifier resin is previously dissolved in a small amount of an organic solvent such as toluene or ethyl acetate, and this is mixed with the curable resin. It is also possible. The mixing ratio of the tackifier resin and the organic solvent is not particularly limited as long as the effect of the present invention is not hindered.

If necessary, ordinary antioxidants, ultraviolet absorbers, plasticizers, fillers, pigments, surfactants, and the like can be appropriately added to the pressure-sensitive adhesive.

Effect of the Invention Since the active energy ray-curable substance of the present invention essentially does not contain a solvent and a reactive diluent, there is a problem of fire danger, pollution, etc., volatilization of the diluent, odor due to unreacted substances. And the like, and can form a cured film excellent in various physical properties, in particular, low-temperature flexibility and heat resistance by irradiation with active energy rays. Further, by changing the irradiation amount of the active energy ray, there is an advantage that the performance of the formed cured film can be arbitrarily adjusted.

Examples Hereinafter, production examples of the active energy ray-curable substance of the present invention will be listed, and further, use examples of the curable substance will be listed.

Production Example 1 Production of Polypropylene Oxide [Component (A)] Having a Reactive Silicon Group Polypropylene oxide having an average molecular weight of 8000 (produced using polypropylene glycol as a starting material. having one) 800 g was taken in a pressure reaction vessel equipped with a stirrer, addition of methyldimethoxysilane 20g, further catalyst solution of chloroplatinic acid _{(H 2 PtCl 6 · 6H 2} O 8.9g of isopropyl alcohol 18m
solution dissolved in l and 160 ml of tetrahydrofuran) 0.34 ml
And reacted at 80 ° C. for 6 hours. When the amount of unreacted silane was quantified by gas chromatography and infrared analysis, it was found that 84% of the terminals had reacted, A polypropylene oxide having a terminal group was obtained.

The weight average molecular weight of the polypropylene oxide is 4200
0 (measured by gel permeation chromatography [manufactured by Nippon Millipore Limited]).

In addition, this polypropylene oxide is Kaneka Cyril
It is commercially available as 5A01 [Kanebuchi Chemical Industry Co., Ltd.].

Production Example 2 Production of active energy ray-curable substance Polypropylene oxide 100 obtained in Production Example 1 above
Were charged in a four-necked flask, and 20 parts of γ-methacryloxypropyltrimethoxysilane A-174 (manufactured by Nippon Unicar Co., Ltd.), 2 parts of water, and a silanol condensation catalyst # 918
After adding 2 parts of [manufactured by Sankyoki Gosei Co., Ltd.] and purging with nitrogen, the mixture was stirred and mixed at 60 ° C. for 6 hours in a nitrogen stream to cause a condensation reaction. The resulting solution is a pale yellow transparent viscous liquid with a viscosity of 10
000 cps [BM viscometer, manufactured by Tokyo Keiki Co., Ltd., 25 ° C., 6 rpm].

The weight average molecular weight of the active energy ray-curable substance obtained above was 42,000, and the glass transition temperature of the curable substance measured by a differential scanning calorimeter (manufactured by Seiko Instruments Inc.) was -69 ° C. there were.

Confirmation of formation of active energy ray-curable substance Polypropylene oxide obtained in Production Example 1 and γ
-Methacryloxypropyltrimethoxysilane A-174
Was determined by measuring the viscosity of the solution, the weight average molecular weight of the condensation reaction product, and the curability of the product by ultraviolet rays by the following method over time.

(1) Viscosity: The viscosity at 25 ° C. and 6 rpm was measured using a BM viscometer.

(2) Weight average molecular weight: The weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography.

(3) Curability: The condensation reaction product was applied to a 25 μm-thick polyester film so that the film thickness after curing became 20 μm, and an ultraviolet irradiation device [Matsushita Electric Works, Ltd., metal halide lamp 80 W / cm, irradiation After irradiating with ultraviolet light at a height of 10 cm and using a dichroic mirror], the films are adhered to each other and evaluated in the state when peeled off. The evaluation criteria are as follows.

 5: Completely hardened without transfer.

 4: Slight fogging is seen in the film.

 3: Partially transferred to film.

 2: Transfer to the whole film.

 1: Cohesive failure, not cured.

The results are shown in Table 1 below. The reaction temperature is 60 ° C.

From the results shown in Table 1 above, the viscosity and the weight average molecular weight immediately after mixing the polypropylene oxide obtained in Production Example 1 and γ-methacryloxypropyltrimethoxysilane A-174, The viscosity and the weight average molecular weight increased with the lapse of time, and the curability of the condensation reaction product was improved. Thus, it was confirmed that the condensation reaction of the two components was progressing.

Use Example 1 Active energy ray-curable substance obtained in Production Example 2 above
100 parts of YS Polystar T-85 [terpene phenol resin, manufactured by Yasuhara Yushi Co., Ltd.] as a tackifier resin and 50 parts of Irgacure 651 as a photosensitizer [manufactured by Ciba Geigy]
Were mixed to obtain a pressure-sensitive adhesive composition.

Use Example 2 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 70 parts of YS Polystar T-85 was used.

Use Example 3 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 90 parts of YS Polystar T-85 was used.

Usage Example 4 The above usage example 1 except that 50 parts of YS Polystar T-100 [terpene phenol resin, manufactured by Yasuhara Yushi Co., Ltd.] is used.
In the same manner as in the above, an adhesive composition was obtained.

Use Example 5 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 70 parts of YS Polystar T-100 was used.

Use Example 6 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 90 parts of YS Polystar T-100 was used.

Usage Example 7 Neopolymer S [Petroleum resin, manufactured by Nippon Petrochemical Co., Ltd.]
Was used in the same manner as in Use Example 1 except that 50 parts of was used to obtain a pressure-sensitive adhesive composition.

Use Example 8 The above use example 1 except that 70 parts of Neopolymer S was used.
In the same manner as in the above, an adhesive composition was obtained.

Use Example 9 The above use example 1 except that 90 parts of Neopolymer S was used.
In the same manner as in the above, an adhesive composition was obtained.

Usage Example 10 The above usage example 1 except that 50 parts of Super Ester A-100 [Rosin ester resin, manufactured by Arakawa Chemical Co., Ltd.] is used.
In the same manner as in the above, an adhesive composition was obtained.

Use Example 11 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 70 parts of Superester A-100 was used.

Use Example 12 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 90 parts of Superester A-100 was used.

Use Example 13 A pressure-sensitive adhesive composition was obtained in the same manner as in Use Example 1 except that 50 parts of Foral 105 (rosin ester resin, manufactured by Hercules) was used.

Use Example 14 The above use example 1 except that 70 parts of Foral 105 are used.
In the same manner as in the above, an adhesive composition was obtained.

Usage Example 15 The above usage example 1 except that 90 parts of Foral 105 are used.
In the same manner as in the above, an adhesive composition was obtained.

Each of the pressure-sensitive adhesive compositions of Use Examples 1 to 15 was applied to a polyester film having a thickness of 25 μm so that the adhesive thickness after drying became 20 μm, and an ultraviolet irradiation device [Matsushita Electric Works, Ltd., metal halide lamp 80 W / cm] , Irradiation height of 10 cm, using a dicool mirror] was irradiated with ultraviolet rays at a speed of 2 m / min to form an adhesive film on the polyester film.

The pressure-sensitive adhesive properties of the pressure-sensitive adhesive sheet thus obtained were examined according to the method described below.

(1) Tack: Measured temperature by J.Dow rolling ball method
Measured at 20 ° C.

(2) Adhesive strength: An adhesive tape was stuck on a stainless steel plate, and after standing for 40 minutes, a 180 ° peel strength was measured at 20 ° C. and 0 ° C. at a peeling speed of 300 mm / min.

(3) Holding force: An adhesive tape was applied to a stainless steel plate in an area of 25 mm × 25 mm, and the time required for the load to fall at a static load of 1 kg and a temperature of 40 ° C. was measured.

 The results are shown in Table 2 below.

As is clear from Table 2, the pressure-sensitive adhesive composition containing the active energy ray-curable substance of the present invention shows excellent pressure-sensitive adhesive properties, particularly excellent low-temperature pressure-sensitive adhesive properties and good heat resistance. . In addition, by changing the type and amount of the tackifying resin, a pressure-sensitive adhesive having various pressure-sensitive adhesive properties can be obtained.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 71/02 C08K 5/54 C09J 171/02

Claims (1)

(57) [Claims] (A) a divalent hydrocarbon having at least one reactive silicon group in the molecule and having a main chain of substantially -RO- (R is a carbon number of 1 to 8) An alkylene oxide polymer having a weight average molecular weight of about 1,000 to about 50,000, and (B) a general formula CH ₂ 2C (CH ₃ ) COO- (R ² ) m-SiZ ₃ [Wherein, R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, m is 0
Or 1, Z represents a hydroxyl group or a hydrolyzable group, respectively. An active energy ray-curable substance obtained by subjecting a compound represented by the formula (1) to a condensation reaction at room temperature or under heating.