KR20150035698A - Curable resin composition, transparent laminate and method for producing transparent laminate - Google Patents

Abstract

A curable resin composition having good transparency and excellent storage stability which is excellent in adhesion between the adherend and the cured resin layer and in the endurance of the cured resin layer and does not change the physical properties of the cured product during the storage period of the oligomer before curing, And a transparent laminate. A reaction product obtained by reacting a polyoxyalkylene polyol (a1), a polyisocyanate (a2) and an unsaturated hydroxy compound (a3) in the presence of an organotin compound or a reaction product obtained by reacting a polyol (a1) and an unsaturated isocyanate (a4) A curable resin composition comprising an unsaturated urethane oligomer (A) as a reaction product, a compound (B) having one curable functional group and one hydroxyl group, a thiol compound (D) and a photopolymerization initiator.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a transparent laminate, and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a curable resin composition capable of obtaining stable cured properties by having excellent storage stability, and a method for producing a transparent laminate using the composition.

It is known that a polyurethane (meth) acrylate oligomer composition can be used for an adhesive resin layer for a transparent laminate having a pair of transparent substrates and an adhesive resin layer sandwiched between the transparent substrates. The curable resin composition for forming such an adhesive resin layer is obtained by reacting a polyurethane (meth) acrylate oligomer obtained by reacting a polyol, isocyanate, and hydroxy (meth) acrylate in the presence of an organotin compound, with monohydroxy (Patent Document 1).

Such a curable resin composition is often stored for a certain period until the curing reaction is carried out.

In addition, recently, the curable resin composition used in the transparent laminate is required to shorten the curing time in order to shorten the production time.

The cured product of the curable resin composition is flexible, and when used as an adhesive layer between the transparent substrates, the yield and tearability with the substrate are good. However, since the curable resin composition contains a highly reactive compound such as monohydroxyalkyl (meth) acrylate, the physical properties of the cured product obtained tend to differ due to the difference in storage period. The tendency becomes remarkable particularly when a monohydroxyalkyl acrylate having high reactivity is contained.

International Publication No. 2010/134547

The present invention provides a curable resin composition having good transparency, excellent adhesion to a transparent substrate and excellent thermal resistance, and excellent storage stability that does not change the physical properties of the cured product during the storage period of the curable resin composition before curing do. The present invention also provides a transparent laminate excellent in adhesion between a transparent substrate and a cured layer of a curable resin composition and a cured layer of a curable resin composition, and a process for producing the same.

The present invention is the invention described in the following [1] to [14].

[1] A curable resin composition comprising the following unsaturated urethane oligomer (A), a compound (B) having one of the following curable functional groups and one hydroxyl group, the following thiol compound (D) and a photopolymerization initiator.

The curable functional _{group: CH 2 = C (R)} C (O) group represented by O- (where, R represents a hydrogen atom or a methyl group).

Unsaturated urethane oligomer (A): an unsaturated urethane oligomer obtained by reacting a polyoxyalkylene polyol (a1), a polyisocyanate (a2) and a compound (a3) having a curing functional group and a hydroxyl group in the presence of an organotin compound, An unsaturated urethane oligomer obtained by reacting an oxyalkylene polyol (a1) and a compound (a4) having the curable functional group and an isocyanate group in the presence of an organotin compound.

Thiol compound (D): a primary thiol compound (D1) having a molecular weight of 70 to 420 per one-SH group or a secondary thiol compound (D2) having a molecular weight of 28 to 420 per one-SH group.

[2] The curable resin composition according to [1], wherein the curable functional group is an acryloyloxy group.

[3] The curable resin composition of [1] or [2], wherein the unsaturated urethane oligomer (A) has an average of 2 to 3 curable functional groups per molecule.

(4) The polyoxyalkylene polyol (a1), wherein the polyoxyalkylene polyol (a1) is poly (oxypropylene.oxyethylene) having an average number of hydroxyl groups of 2 to 3, a hydroxyl value of 15 to 30 mgKOH / g and an oxyethylene group content of 8 to 50% The curable resin composition according to any one of [1] to [3], which is a polyol.

[5] The curable resin composition according to any one of [1] to [4], wherein the polyisocyanate (a2) is an alicyclic diisocyanate or an aliphatic diisocyanate.

[6] The curable resin composition according to any one of [1] to [5], wherein the compound (a3) is a hydroxyalkyl acrylate having a hydroxyalkyl of 2 to 12 carbon atoms.

[7] The curable resin composition according to any one of [1] to [6], wherein the organotin compound is an organic tin carboxylate.

[8] The curable resin composition according to any one of [1] to [7], wherein the compound (B) is a monohydroxyalkyl acrylate having a hydroxyalkyl having 3 to 8 carbon atoms.

[9] The curable resin composition according to any one of [1] to [8], wherein the thiol compound (D1) is an aliphatic thiol compound.

[10] The curable resin composition according to any one of [1] to [8], wherein the thiol compound (D2) is an aliphatic thiol compound having 3 to 40 carbon atoms or an alicyclic thiol compound having 3 to 40 carbon atoms.

[11] The curable resin composition according to any one of [1] to [10], further comprising a compound (C) having one curable functional group and an alkyl group having 8 to 22 carbon atoms.

[12] The curable resin composition according to any one of [1] to [3], wherein the curable resin composition contains 20 to 75% by mass of the unsaturated urethane oligomer (A), 10 to 50% by mass of the compound (B) and 0.05 to 3.0% by mass of the thiol compound (D) 11]. ≪ / RTI >

[13] A transparent laminate having a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates, wherein the cured resin is a transparent laminate as a cured product of the curable resin composition of any one of [1] to [12] .

[14] A method for producing a light-emitting device, comprising the steps of: forming a curable resin composition layer of any one of the above-mentioned [1] to [12] on one transparent substrate, overlapping another transparent substrate on the curable resin composition layer in a reduced- A first step of producing a lamination precursor having the curable resin composition sealed between a transparent substrate of the transparent substrate and the pair of transparent substrates,

And a second step of curing the curable resin composition under an atmosphere in which the lamination precursor is placed in an atmosphere having a higher pressure than the pressure-reduced atmosphere.

According to the curable resin composition of the present invention, it is possible to obtain a curable resin composition having little change in the physical properties of the cured product during the storage period of the composition before curing.

1 is a cross-sectional view showing a step in the production of a transparent laminate.

The curable functional group represented by CH ₂ ═C (R) C (O) O- (wherein R represents a hydrogen atom or a methyl group) in the present specification is an acryloyloxy group (when R is a hydrogen atom) (When R is a methyl group), and the group represented by the formula is hereinafter also referred to as a (meth) acryloyloxy group. Similarly, "(meth) acrylate" is used as a generic term of "acrylate" and "methacrylate".

<Curable resin composition>

The curable resin composition of the present invention is a curable resin composition containing an unsaturated urethane oligomer (A). Since the curable resin composition is excellent in transparency, and has excellent adhesion with a transparent substrate and excellent thermal resistance, a curable resin And is preferable as a curable resin composition used in a method for producing a transparent laminate by curing the composition.

(Unsaturated urethane oligomer (A))

The unsaturated urethane oligomer (A) is an unsaturated urethane oligomer obtained by reacting a polyoxyalkylene polyol (a1), a polyisocyanate (a2), and a compound (a3) having a curable functional group and a hydroxyl group in the presence of an organotin compound, Is an unsaturated urethane oligomer obtained by reacting an alkylene polyol (a1) and a compound (a4) having a curable functional group and an isocyanate group in the presence of an organotin compound. Hereinafter, the unsaturated urethane oligomer (A) is also referred to as an oligomer (A).

The number of curable functional groups of the unsaturated urethane oligomer (A) is preferably 2 to 3 on average per molecule. The number of curable functional groups of the oligomer (A) can be adjusted by the number of curable functional groups of the compound (a3) or the compound (a4), the number of hydroxyl groups of the polyoxyalkylene polyol (a1), the number of isocyanate groups of the polyisocyanate (a2) .

For example, a polyoxyalkylene polyol having an average number of hydroxyl groups of 2 to 3, a diisocyanate and a monohydroxyalkyl (meth) acrylate, or a polyoxyalkylene polyol having an average number of hydroxyl groups of 2 to 3 with a monoisocyanate alkyl ) Acrylate, oligomers (A) having a number of average curing functional groups of 2 to 3 can be prepared. In addition, polyoxyalkylene diols and diisocyanates and hydroxyalkyl (meth) acrylates having an average number of curable functional groups of more than 1 and not more than 1.5 (for example, dihydroxyalkyl (meth) acrylate and monohydroxyalkyl Acrylate), an oligomer (A) having an average number of curable functional groups of more than 2 but not more than 3 can be produced.

Examples of the oligomer (A) include a polyoxyalkylene polyol having an average number of hydroxyl groups of 2 to 3 as the polyoxyalkylene polyol (a1), a diisocyanate as the polyisocyanate (a2), and one curable functional group and one hydroxyl group as the compound (a3) And an unsaturated urethane oligomer obtained by using a compound having one curable functional group and one isocyanate group as the compound (a4).

The proportion of the oligomer (A) is preferably 20 to 75 mass%, more preferably 40 to 60 mass%, in 100 mass% of the curable resin composition. When the proportion of the oligomer (A) is 20 mass% or more, the cured product is not deformed well even when exposed to high temperatures. When the proportion of the oligomer (A) is 75% by mass or less, the cured product is not well retracted.

(Polyoxyalkylene polyol (a1))

The average number of hydroxyl groups of the polyoxyalkylene polyol (a1) is preferably 2 to 4. In order to prepare the oligomer (A) having an average number of curable functional groups of 2 to 3, the average number of hydroxyl groups of the polyoxyalkylene polyol (a1) is preferably 2 to 3.

Hereinafter, the polyoxyalkylene polyol (a1) is also referred to as polyol (a1).

The hydroxyl value of the polyol (a1) is preferably 15 to 30 mgKOH / g. When the hydroxyl value is 15 mgKOH / g or more, the strength of the cured product becomes good. Further, since the molecular weight is not excessively increased, the viscosity of the polyol (a1) is not excessively increased, and the workability is not problematic. When the hydroxyl value of the polyol (a1) is 30 mgKOH / g or less, the cured product can maintain high flexibility.

The hydroxyl value of the polyol (a1) is measured according to JIS K1557-1 (2007 edition). The hydroxyl groups of other polyols are also the same.

The polyol (a1) is prepared by reacting an alkylene oxide with an initiator having an active hydrogen in the presence of a catalyst.

Examples of the catalyst include diethylzinc, iron chloride, metal porphyrin, complex metal cyanide complex, cesium compound, alkali (earth metal) compound and the like, and an alkali metal compound catalyst or a complex metal cyanide complex is preferable, Cyanide complexes are particularly preferred. When a polyoxyalkylene polyol having a low hydroxyl value is obtained by reacting propylene oxide with a general-purpose alkali metal compound catalyst (such as potassium hydroxide), the isomerization reaction of propylene oxide tends to occur and the degree of unsaturation increases. The cured product containing the oligomer (A) obtained by using the polyoxyalkylene polyol having a high degree of unsaturation may have insufficient mechanical properties. The degree of unsaturation (USV) of the polyol (a1) is preferably 0.05 or less.

Therefore, in order to prepare the polyol (a1) having a low hydroxyl value, it is preferable to use a complex metal cyanide complex catalyst. On the other hand, it is difficult for the composite metal cyanide complex catalyst to react with ethylene oxide alone. Therefore, in the case of producing a block copolymer type polyoxyalkylene polyol, it is preferable to react monoepoxide having a carbon number of 3 or more with a composite metal cyanide complex catalyst and then react with ethylene oxide using another catalyst Do.

As complex metal cyanide complexes, complexes containing zinc hexacyanocobaltate as a main component are preferable, and ether and / or alcohol complexes of zinc hexacyanocobaltate are particularly preferable. Examples of the ether and / or alcohol complex of zinc hexacyanocobaltate include those described in Japanese Patent Publication No. 46-27250. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether and the like are preferable, and glyme is particularly preferable from the viewpoint of easy handling in the production of the complex. As the alcohol, tert-butanol, tert-butyl cellosolve and the like are preferable.

One type of initiator may be used alone, or two or more types may be used in combination. When two or more species are used, the number of active hydrogen atoms in the initiator is represented by the average number of active hydrogen atoms. The average number of active hydrogens of the initiator is preferably 2 to 4, more preferably 2 to 3. The active hydrogen refers to a hydrogen atom that is capable of reacting with an alkylene oxide such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group. As the active hydrogen, a hydrogen atom of a hydroxyl group is preferable. Therefore, as the initiator, a polyhydric alcohol having an average number of hydroxyl groups of 2 to 4 is preferable, and a polyhydric alcohol having an average number of hydroxyl groups of 2 to 3 is more preferable. Examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, And a polyoxyalkylene polyol having a lower molecular weight than that of the intended polyoxyalkylene polyol. When a complex metal cyanide complex is used, the molecular weight of the initiator is preferably 500 to 1,500, and particularly preferably a polyoxypropylene polyol having a molecular weight of 500 to 1,500 obtained by reacting propylene oxide with a polyhydric alcohol having 2 to 4 valences.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide and the like. One of them may be used alone, or two or more of them may be used in combination.

Of the alkylene oxides, ethylene oxide and propylene oxide are preferred. It is more preferable to use ethylene oxide and propylene oxide in combination.

As the polyol (a1), a block copolymer type polyoxyalkylene polyol obtained by reacting propylene oxide with an initiator and then with ethylene oxide, or a random copolymer type obtained by reacting an initiator with a mixture of propylene oxide and ethylene oxide A polyoxyalkylene polyol is preferable, and a former block copolymer type polyoxyalkylene polyol is particularly preferable.

The average number of hydroxyl groups per molecule of the polyol (a1) is the number of active hydrogen per molecule of the initiator when the initiator is one, and when the initiator is a mixture of two kinds, the number of active water per molecule of the initiator It is a prime number average.

The polyol (a1) is preferably a poly (oxypropylene.oxyethylene) polyol having an average number of hydroxyl groups of 2 to 3, a hydroxyl value of 15 to 30 mgKOH / g and an oxyethylene group content of 8 to 50 mass% ) Or a mixture of the polyol (a11) and the other polyol (hereinafter referred to as the polyol (a12)).

The content of the polyol (a11) in the polyol (a1) is preferably 30 to 100 mass%, more preferably 60 to 100 mass%. When the polyol (a11) is 30 mass% or more, the cured product is excellent in flexibility and transparency.

When the content of the oxyethylene group in the polyol (a11) is 8 mass% or more, the compatibility of the oligomer (A) with the reactive component such as the compound (B) becomes good and the transparency of the cured product becomes good. When the content of the oxyethylene group is 50 mass% or less, the crystallinity of the molecule (s) is relaxed to become a liquid at room temperature, so that the handling becomes easy, and the workability is not problematic.

The oxyethylene group content of the polyol can be calculated from the peak of the ¹ H-NMR (nuclear magnetic resonance) spectrum.

(Polyol (a12))

The polyol (a12) is a polyol other than the polyol (a11). Examples of the polyol (a12) include a polyoxyalkylene polyol having no oxyethylene group, a polyoxyalkylene polyol having an average number of hydroxyl groups of more than 3, a polyoxyalkylene polyol having a hydroxyl value of more than 30 mgKOH / g And the like.

(Polyisocyanate (a2))

Examples of the polyisocyanate (a2) include alicyclic polyisocyanates having an average number of isocyanate groups per molecule of 2 or more, aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates, and modified polyisocyanates obtained by modifying them. It is preferable that the aromatic polyisocyanate having an isocyanate group bonded to the aromatic ring is not used because it is highly likely to cause yellowing of the cured resin.

The average number of isocyanate groups per molecule of the polyisocyanate (a2) is preferably from 2 to 4, and particularly preferably 2. [ That is, as polyisocyanate (a2), diisocyanate is preferable. The polyisocyanate (a2) may be used singly or in combination of two or more.

Specific examples of the polyisocyanate (a2) include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, prepolymer-modified products of the diisocyanates thereof, , Urea-modified products, and carbodiimide-modified products, and isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.

The amount of the polyisocyanate (a2) relative to the polyol (a1) is preferably an isocyanate index (also referred to as INDEX) of 1.03 to 1.45, and more preferably 1.05 to 1.25.

The isocyanate index is a value obtained by dividing the equivalence of the isocyanate group of the polyisocyanate by the equivalent of the hydroxyl group.

(Compound (a3))

The compound (a3) is a compound having a curable functional group and a hydroxyl group, and two or more curable functional groups may be present in one molecule, or two or more hydroxyl groups may be present in one molecule. In order to prepare the oligomer (A) having an average of 2 to 4 curable functional groups, a compound having one curable functional group and one hydroxyl group in one molecule is preferable.

Compound (a3), the hydroxyalkyl (meth) acrylate, i.e., _{CH 2 = C (R) C} (O) OR ⁴ the compound represented by -OH with a hydroxyalkyl having a carbon number of 2 to 12 (however, R ⁴ Represents an alkylene group having 2 to 12 carbon atoms). R ⁴ is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms. In order to obtain the highly reactive oligomer (A), the curable functional group is preferably an acryloyloxy group (R is a hydrogen atom). Accordingly, as the compound (a3), a hydroxyalkyl acrylate having a hydroxyalkyl of 2 to 12 carbon atoms is more preferable, and a hydroxyalkyl acrylate having a hydroxyalkyl of 2 to 4 carbon atoms is particularly preferable.

Specific examples of the compound (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, -Hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferable. The compound (a3) may be used alone or in combination of two or more.

(Compound (a4))

The compound (a4) is a compound having a curable functional group and an isocyanate group, and two or more curable functional groups may be present in one molecule, and two or more isocyanate groups may exist in one molecule. In order to prepare the oligomer (A) having an average of 2 to 4 curable functional groups, a compound having one curable functional group and one isocyanate group in one molecule is preferable.

As the compound (a4), a compound represented by CH ₂ ═C (R) C (O) OR ⁵ -NCO (wherein R ⁵ represents an alkylene group having 1 to 6 carbon atoms) is particularly preferable. In order to obtain the highly reactive oligomer (A), R is preferably a hydrogen atom. R ⁵ is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms. The compound (a4) may be used alone or in combination of two or more.

Specific examples of the compound (a4) include 2-isocyanatoethyl methacrylate (Carlens MOI (trade name), manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate ) Manufactured by Showa Denko KK).

When the polyol (a1) is reacted with the compound (a4), the isocyanate index is preferably 0.95 to 1.02, more preferably 0.98 to 1.00.

The oligomer (A) can be produced from the polyol (a1), the polyisocyanate (a2) and the compound (a3) or the polyol (a1) and the compound (a4).

For example, the polyol (a1) and the polyisocyanate (a2) are mixed in an amount of 1.03 to 1.45 with INDEX and reacted in the presence of an organotin compound to obtain an urethane prepolymer having an isocyanate group. The compound (a3) may be further added, and if necessary, an organic tin compound may be further added to react.

The polyol (a1) and the compound (a4) may be prepared by mixing the polyol (a1) and the compound (a4) so that the INDEX is from 0.95 to 1.02 and reacting in the presence of an organotin compound.

(Organotin compound)

The organotin compound is used as a reaction catalyst between the polyol (a1), the polyisocyanate (a2) and the compound (a3), and the reaction between the polyol (a1) and the compound (a4).

Examples of the organic tin compound include divalent tin compounds such as 2-ethylhexanoate tin, tin naphthenate, and tin stearate; Organic tin carboxylate such as dialkyltin dicarboxylate or dialkoxy tin monocarboxylate such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin monoacetate, and dibutyltin maleate, di Tin chelate compounds such as alkyl tin bisacetylacetonate and dialkyltin monoacetylacetonato monoalkoxide, reaction products of dialkyltin oxide and ester compounds, reactants of dialkyltin oxide and alkoxysilane compounds, dialkyltin dialkyl sulfide And the like.

Examples of the tin chelate compounds include dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetate, dibutyltin monoacetylacetonate monoalkoxide, and the like.

Of these, organotin carboxylic acid salts are preferable from the viewpoint of the reactivity of the urethanization reaction, and among them, from the viewpoints of the reactivity and ease of handling of the urethanization reaction and hydrolysis resistance, dibutyltin dilaurate, The rate is more preferred.

The organotin compound is preferably contained in an amount of 0.0005 to 0.05 mass%, more preferably 0.010 to 0.03 mass%, based on the oligomer (A). If it is 0.005 mass% or more, it is preferable from the viewpoint of the reactivity of the urethanization reaction, and if it is 0.05 mass% or less, rapid gelation in the urethane reaction is prevented.

(Compound (B))

The compound (B) is a compound having one curable functional group and one hydroxyl group, that is, a (meth) acrylate having one hydroxyl group in one molecule. If the hydroxyl group is contained in one molecule, the adhesion of the cured product to the adherend is good, and the physical properties of the cured product are good.

The compound (B) is a compound represented by the formula CH ₂ C (R) C (O) OR ² -OH (wherein R ² represents an alkylene group). R ² is preferably an alkylene group having 3 to 8 carbon atoms. The compound (B) is preferably an acrylate compound which is a compound having a fast reaction. The compound (B) is effective as a component for increasing the hydrophilicity of the cured product of the curable composition to improve the affinity between the cured product and the surface of the adherend, and the adhesion between the cured product and the transparent substrate is improved by using the compound (B). The strength of the cured product is also improved.

When the carbon number of R ² is 3 or more, the transparency of the cured product becomes good. When the carbon number of R ² is 8 or less, sufficient adhesion is obtained. The carbon number of R ² is more preferably 3 to 6.

The compound (B) may be used alone or in combination of two or more.

Examples of the compound (B) include 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 2- 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and 6-hydroxyhexyl acrylate. From the viewpoints of high transparency and high reactivity of the resulting curable resin composition, 2-hydroxybutyl acrylate .

The compound (B) is preferably contained in an amount of 10 to 50 mass%, more preferably 25 to 45 mass%, of 100 mass% of the curable resin composition. When it is 25 mass% or more, it is preferable from the viewpoint of adhesion to the substrate, and when it is 50 mass% or less, it is preferable from the viewpoint of flexibility and transparency of the cured product.

(Thiol compound (D))

The thiol compound (D) is a compound having at least one -SH group. Secondary thiol compounds, and tertiary thiol compounds by the number of substituents of the carbon atoms to which the -SH group is bonded.

The thiol compound (D) in the present invention is a thiol compound selected from the following thiol compounds (D1) and thiol compounds (D2).

Thiol compound (D1): A primary thiol compound having a molecular weight per one-SH group of 70 to 420.

Thiol compound (D2): A secondary thiol compound having a molecular weight of 28 to 420 per one-SH group.

The thiol compound (D1) and the thiol compound (D2) may be used in combination as the thiol compound (D), or two or more kinds thereof may be used in combination as the thiol compound (D1) .

The molecular weight per one-SH group of the thiol compound (D1) is preferably 130 to 280, more preferably 200 to 250. If it is 70 or more, the change in physical properties of the cured product after storage of the curable resin composition is small, and the physical properties of the cured product are good. If it is 420 or less, it is easy to obtain.

The molecular weight per one-SH group of the thiol compound (D2) is preferably 42 to 280, more preferably 50 to 250, and particularly preferably 70 to 250. When it is 28 or more, changes in physical properties of the cured product after storage of the curable resin composition are small, and the physical properties of the cured product are good. If it is 420 or less, it is easy to obtain.

It is presumed that the thiol compound (D) in the present invention acts on the organotin compound in the curable resin composition to improve the storage stability. On the other hand, since the thiol compound also acts as a chain transfer agent, the physical properties of the cured product become better, so that the action as a chain transfer agent is preferably as small as possible.

The number of -SH groups contained in one molecule of the thiol compound (D) is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 4. When the number of -SH groups in one molecule is 1 or more, good storage stability is obtained. When the number of -SH groups is 5 or less, commercial products are easily available and storage stability is good. In any of the primary and secondary thiol compound (D), the smaller the molecular weight per one-SH group is, the more easily the effect of the storage stability tends to be obtained.

The thiol compound (D1) includes an aliphatic primary thiol having 5 to 40 carbon atoms, more preferably 5 to 30 carbon atoms, and particularly preferably 5 to 20 carbon atoms. Examples of the thiol compound (D2) include an aliphatic secondary thiol having 3 to 40 carbon atoms and an alicyclic secondary thiol having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and 5 to 20 carbon atoms Particularly preferred. These compounds may have branching in the molecular chain not bonded to the -SH group. The thiol compound (D) is liable to have an effect of storage stability as the carbon number is smaller in both the first and second classes.

As the first- or second-level aliphatic thiol compound, an alkane thiol and an ester of a carboxylic acid containing a -SH group and an alcohol having a monovalent to polyhydric alcohol are preferable. Examples of the -SH group-containing carboxylic acid include thioglycolic acid and 3-mercaptobutanoic acid.

Specific examples of the aliphatic primary thiol include 1-pentanethiol, 1-decanethiol; 1-dodecanethiol (thiocarcoyl 20 (trade name) manufactured by Kao Corporation), 1-hexadecanethiol, 1-octadecanethiol and 1,6-hexanediol bis (thioglycolate). Examples of the alicyclic secondary thiol include cyclopentanethiol and cyclohexanethiol. Examples of the aliphatic secondary thiol include 2-decanthiol, pentaerythritol tetrakis (3-mercaptobutyrate) 1,4-bis (3-mercaptobutyryloxy) butane (Carlens MT (registered trademark) BD1 (trade name): Showa Denko Co., Ltd.) and the like.

The thiol compound (D) is contained preferably in an amount of 0.05 to 3.0 mass%, more preferably 0.1 to 2.0 mass%, in 100 mass% of the curable resin composition. When it is 0.05 mass% or more, it is preferable from the viewpoint of storage stability, and when it is 3.0 mass% or less, the photo-curing reactivity and the strength property of the cured product of the curable resin composition become good.

Since the thiol compound (D1) has a higher reactivity with the thiol group than the thiol compound (D2), the effect of the storage stability can be obtained in a smaller amount. However, if the thiol compound (D1) is blended too much, the storage stability of the curable resin composition There is a possibility of causing a problem due to a metering error. Thiol compound (D2) may need more amount than thiol compound (D1), but the problem due to metering error does not occur well. Therefore, when the thiol compound (D1) is used as the thiol compound (D), a relatively small amount is used in the above range of use, and when the thiol compound (D2) is used, a relatively large amount of the above range of use is preferably used .

When the thiol compound (D1) and the thiol compound (D2) are used in combination, the content ratio thereof is not particularly limited, but it is preferable to change the content ratio of the thiol compounds (D1) and (D2) according to the purpose.

(Photopolymerization initiator)

When the curable resin composition of the present invention contains a photopolymerization initiator, it becomes a curable resin composition which can be cured by light irradiation.

The photopolymerization initiator is preferably excited by irradiation with visible light or ultraviolet light (wavelength: 300 to 400 nm) to activate and accelerate the curing reaction, and a benzoin ether-based photopolymerization initiator, an? -Hydroxyalkylphenone- A photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator.

Specific examples of the photopolymerization initiator include benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzo Hydroxybutyl ether, benzoin isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- 2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- , 6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferable, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferable since they can sufficiently cure the curable resin composition even in the case of adding a very small amount Acylphosphine oxide And a radical photopolymerization initiator is particularly preferable. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

The content of the photopolymerization initiator is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 2.5 parts by mass, per 100 parts by mass of the oligomer (A).

(Other components)

The curable resin composition containing the unsaturated urethane oligomer (A) can be used for adhesives, coating agents, and other uses. Various additives may be added to the curable resin composition depending on the application.

As the curing agent for curing the curable resin composition, a thermal polymerization initiator for generating a radical by heat may be further contained. By further containing a thermal polymerization initiator, it becomes a photo-curable type and a thermosetting type. In the method of producing a transparent laminate, which will be described later, by forming a photo-curable type and a thermosetting type, curing can be promoted by thermosetting even when a light shielding portion is formed on the transparent substrate and portions where light is not easily transmitted.

(Curable resin composition preferable for production of transparent laminate)

The curable resin composition used in the method for producing the transparent laminate of the present invention preferably further contains a compound (C) having one curable functional group and an alkyl group having 8 to 22 carbon atoms. The compound (C) is a compound having no hydroxyl group. A compound having a curable functional group other than the oligomer (hereinafter referred to as oligomer (E)), the compound (B) and the compound (C) other than the oligomer (A) ), A thiol compound (D) and an additive other than the polymerization initiator (hereinafter referred to as additive (G)).

When the oligomer (E), the compound (F) or the additive (G) is contained in the curable resin composition, the proportion thereof is preferably 10 mass% or less, more preferably 5 mass% or less, .

(Compound (C))

The compound (C) is a compound represented by CH ₂ ═C (R) C (O) OR ³ (wherein R ³ represents an alkyl group having 8 to 22 carbon atoms). Two or more compounds (C) may be used in combination.

When the curable resin composition contains the compound (C), the modulus of the cured product is lowered, and the thermostability is easily improved. When the number of carbon atoms in the alkyl group is 8 or more, the volatility is low and the glass transition temperature of the cured product can be lowered. If the carbon number of the alkyl group is 22 or less, it is readily available.

As the compound (C), there may be mentioned n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate, n-dodecyl acrylate, n-octadecyl acrylate, , Lauryl acrylate and the like, and lauryl acrylate is particularly preferable.

When the curable resin composition contains the compound (C), the content of the compound (C) is preferably 3 to 50% by mass, and more preferably 5 to 25% by mass. When the content of the compound (C) is 3% by mass or more, the flexibility of the cured product becomes good.

(Oligomer (E))

The curable resin composition of the present invention may contain a small amount of an oligomer (E) for the purpose of adjusting physical properties of the resulting cured product.

Examples of the oligomer (E) include urethane (meth) acrylate oligomer obtained by using a polyol other than the polyol (a1), poly (meth) acrylate of a polyoxyalkylene polyol, poly (meth) acrylate of a polyester polyol, .

(Compound (F))

The curable resin composition of the present invention may contain a small amount of a compound (F) ((meth) acrylates, etc.) having at least one curable functional group for the purpose of adjusting physical properties of the resulting cured product. Examples of the compound (F) include poly (meth) acrylates of polyhydric alcohols.

When the curable resin composition of the present invention is used in the vacuum lamination method, alkyl (meth) acrylates having a low alkyl group as the compound (F) can not be used for the following reasons. However, when the curable resin composition of the present invention is used in a method other than the vacuum lamination method, the compound (F) may be an alkyl (meth) acrylate having a lower alkyl group carbon number.

When the curable resin composition is used for producing a transparent laminate by a vacuum lamination method described later, it is not preferable that the curable resin composition contains a compound having a low boiling point. In the vacuum lamination method, the curable resin composition is exposed to a reduced pressure in a state where the curable resin composition is diffused on substantially the entire surface excluding the periphery of the transparent substrate. When the curable resin composition contains a compound having a low boiling point, , There is a possibility that the composition of the curable resin composition changes greatly. In addition, it is difficult to maintain the reduced pressure atmosphere at a required reduced pressure by the volatilization of the volatile compounds.

On the other hand, in the method in which a liquid curable resin composition is injected between a pair of transparent substrates sealed in the periphery and cured, even when injected at a reduced pressure between the transparent substrates, the curable resin composition exposed to the reduced pressure at the time of injection The area of the surface is narrow and the degree of decompression does not need to be so high that even if the curable resin composition contains a compound having a relatively low boiling point, the volatilization becomes less of a problem.

The component which is liable to have a low boiling point in the curable resin composition is a relatively low molecular weight compound having one curable functional group. The compound (B) is a hydroxyalkyl (meth) acrylate, and its boiling point is sufficiently high. The compound (C) has a high boiling point because the number of carbon atoms of the alkyl group is large even when alkyl (meth) acrylate is used. The alkyl (meth) acrylate having a low alkyl group has a low boiling point, and the curable resin composition containing such an alkyl (meth) acrylate having a low boiling point can be used as a curable resin composition for producing a transparent laminate by a vacuum lamination method I can not. The curable resin composition that can be used in the pressure-sensitive lamination method preferably contains no compound having a boiling point of normal pressure of 150 占 폚 or lower, preferably 200 占 폚 or lower.

(Additive (G))

Examples of the additive (G) include ultraviolet absorbers (benzotriazole-based, hydroxyphenyltriazine-based), light stabilizers (such as hindered amines), pigments, dyes, metal oxide fine particles and fillers.

The ultraviolet absorber is used for preventing light deterioration of the curable resin composition and improving weather resistance, and examples thereof include ultraviolet absorbers such as benzotriazole series, triazine series, benzophenone series and benzoate series.

Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4-bis (1-methyl- 2-benzotriazolyl) -6-tert-butyl-p-cresol, 2- (2-hydroxy- (2,2-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] 2-yl) -4,6-bis (1,1-dimethyl-propyl) -phenol.

Examples of the triazine-based ultraviolet absorber include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol, 2- [ -Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (isooctyloxy) -phenol.

Examples of the benzophenone ultraviolet absorber include 2-hydroxy-4-n-octyloxybenzophenone and (2,4-dihydroxyphenyl) phenyl-methanone.

Examples of the benzoate ultraviolet absorber include 2- [4,6-diphenyl-1,3,5-triazin-2-yl] -5- (hexyloxy) phenol and the like.

The light stabilizer is used for preventing light deterioration of the curable resin composition and improving weather resistance. For example, a light stabilizer based on a hindered amine may be mentioned.

Examples of hindered amine-based light stabilizers include the following compounds.

N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -N'- [4- [butyl (2,2,6,6-tetramethyl-4-piperidinyl ) Amino] -1,3,5-triazin-2-yl] -1, 6-hexanediamine, butane diacid 1- [2- (4-Hydroxy-2,2,6,6-tetramethylpiper Dino) ethyl], 2-butyl-2- (4-hydroxy-3,5-di- tert -butylbenzyl) malonic acid bis (1,2,2,6,6-pentamethylpiperidin- (1,2,2,6,6-pentamethylpiperidin-4-yl), decanedic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) Butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), 1,2,3,4-butanetetracarboxylic acid Tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-pentamethylpiperidin-4-yl), 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 7-oxa-3,20-diazadis [ [5.1.11.2] heneicanoic acid-20-propanoic acid To a solution of 2,2,4,4-tetramethyl-21-oxo-dodecyl / tetradecyl 2,2,4,4-tetramethyl-7-oxa-3,20 diazadis pyrro [5.1.11.2] -hexenoic acid-21-one, beta -alanine N- (2,2,4,4 - tetradecyl-4-piperidinyl) -dodecyl / tetradecyl ester, 2,5-pyrrolidinedione 3-dodecyl-1- (2,2,6,6- ), 2,5-pyrrolidinedione N-acetyl-3-dodecyl-1- (2,2,6,6-tetra-methyl-4-piperidinyl).

The antioxidant is used for preventing oxidation of the curable resin composition and improving weather resistance and heat resistance, and examples thereof include phenolic antioxidants and phosphorus antioxidants.

Examples of the phenol-based antioxidant include the following compounds.

(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N ' Bis [1,1-dimethylethyl) -4-hydroxybenzenepropanamide], octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, 2,4,6 -Tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, calcium bis [3,5-di (tert- butyl) -4-hydroxybenzyl (ethoxy) (Octylthiomethyl) -6-methylphenol, bis [3- (1,1-dimethylethyl) - 4-hydroxy-5-methylbenzenepropionic acid] ethylenebis (oxy-2,1-ethanediyl), 1,6-hexanediol-bis [3- (3,5- ) Propionate], 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphe ] Methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, 1,1'-iminobi [4- (1,1,3,3-tetramethyl Butyl] benzene], 4 - [[4,6-bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-di- 3,5-bis (1,1-dimethylethyl) -4-hydroxylphenyl] methyl} phosphonate.

Examples of the phosphorus antioxidant include the following compounds.

(3-methyl-6-tert-butylphenyl dontridecyl) phosphite, cyclic neopentylsulfonate, cyclopentylphosphite, cyclopentylphosphite, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'- (Nonylphenyl) phosphite, cyclic neopentane tetraylbis (dinonylphenyl) phosphite, cyclic neopentane tetrayltris (nonylphenyl) phosphite, cyclic neopentane tetrayltris (dinonyl Phenylphosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tris (2-tert-butyl-5-methyl-4-methylphenyl) phosphite, bis (2,4-di-tert- 1-phenylene) oxy] bis (ditridecylphosphonate).

The curable resin composition of the present invention described above contains the oligomer (A), the compound (B), the thiol compound (D) and the photopolymerization initiator obtained by using the polyol (a1) It is possible to obtain a curable resin composition having little change in the physical properties of the cured product due to the period.

<Transparent laminate>

The transparent laminate of the present invention has a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates. The cured resin layer is a layer comprising a cured product of the curable resin composition of the present invention.

As the transparent substrate, a glass plate or a resin plate can be given. When a glass plate is used, a lumber glass is obtained. When a polycarbonate plate is used as the resin plate, a transparent panel having high impact resistance and light weight can be obtained. A glass plate and a resin plate may be used in combination.

The size of the transparent substrate is not particularly limited, but a transparent substrate having at least one side of 300 mm or more, more preferably 600 mm or more, can be widely used as a transparent member provided in an opening for building or automobile. For typical applications, a size of 4 m 2 or less is suitable.

The thickness of the cured resin layer is preferably 0.2 to 4.0 mm. When the thickness of the cured resin layer is 0.2 mm or more, the mechanical strength of the transparent laminate becomes good.

In the transparent laminate of the present invention described above, since the cured resin layer sandwiched between the transparent substrates is composed of the cured product of the curable resin composition of the present invention, the transparency is good and the adhesion between the transparent substrate and the cured resin layer, It is excellent in resistance to seizure and shock absorption.

&Lt; Method of producing transparent laminate >

The transparent laminate of the present invention can be produced by a known production method (for example, a method of sandwiching a curable resin composition between a pair of transparent substrates and curing the curable resin composition) Is preferably produced by the production method according to the present invention. The vacuum lamination process is described in WO 08/081838 or WO 09/016943.

The pressure-sensitive lamination method is characterized in that a curable resin composition layer is formed on one transparent substrate, another transparent substrate is superimposed on the curable resin composition layer in a reduced-pressure atmosphere, the curable resin composition is sealed between the two transparent substrates , And then putting it in a pressure atmosphere (usually atmospheric pressure atmosphere) higher than the pressure-reduced atmosphere to cure the curable resin composition. Therefore, the method for producing a transparent laminate of the present invention requires the following first step and second step.

Step 1: A curable resin composition layer is formed on one transparent substrate, and another transparent substrate is superimposed on the curable resin composition layer in a reduced pressure atmosphere, and a pair of transparent substrates and a pair of transparent substrates A process for producing a laminated precursor having the above-mentioned curable resin composition sealed.

Step 2: A step of placing the lamination precursor in an atmosphere having a pressure higher than that of the reduced-pressure atmosphere, and curing the curable resin composition under the atmosphere.

The reduced pressure atmosphere in the first step is preferably 1 atmosphere or less, more preferably 100 Pa or less. When the pressure in the reduced pressure atmosphere is too low, a pressure atmosphere of 1 Pa or more is preferable, and a pressure atmosphere of 10 Pa or more is more preferable because a reduced pressure component in the curable resin composition may be volatilized. Do.

In an atmosphere having a higher pressure than the pressure-reduced atmosphere in the second step, a pressure atmosphere of 50 kPa or more is preferable, and a pressure atmosphere of 100 kPa or more is more preferable. The pressure atmosphere in the second step is usually an atmospheric pressure atmosphere. Hereinafter, this manufacturing method will be described as an example where the atmosphere having a pressure higher than that of the reduced-pressure atmosphere is an atmospheric pressure atmosphere.

In the first step, even if bubbles remain in the curable resin composition in the closed space, the bubbles are liable to disappear before the curable resin composition is cured, and it is easy to obtain a cured resin layer free from air bubbles. That is, when the lamination precursor formed in the first step is left under atmospheric pressure, pressure is applied also to the curable resin composition in the closed space by the pressure from the transparent substrate under atmospheric pressure. On the other hand, since the inside of the bubble in the curable resin composition is in a reduced-pressure atmosphere pressure in the first step, the volume of the bubble is reduced by the pressure applied to the curable resin composition in the second step, So that the bubbles disappear. In order to eliminate bubbles, it is preferable to maintain the lamination precursor under atmospheric pressure for a while before curing the curable resin composition. The holding time is preferably 5 minutes or more. However, the holding time may be shorter in the case where there is no air bubble or when the air bubble is small and disappears quickly.

In the first step, the reduced-pressure atmosphere is required in the step of forming the closed space, and is not required in the preceding step. For example, when a sealing material having a predetermined thickness is formed around the entire periphery of one surface of one transparent substrate and a curable resin composition is supplied to the surface of the transparent substrate surrounded by the sealing material to form the curable resin composition layer, In the step, it can be carried out in an atmospheric pressure atmosphere. The formation of the closed space is preferably carried out as follows.

The transparent substrate having the curable resin composition layer obtained as described above and the other transparent substrate are placed in a decompression chamber to have a predetermined arrangement. That is, the transparent substrate having the curable resin composition layer is placed on a horizontal platen with the curable resin composition layer up, and the other transparent substrate is mounted on the lower surface of the horizontal platen mounted on the end of the cylinder , And both of the transparent substrates are placed in parallel without contacting the other transparent substrate with the curable resin composition layer. Thereafter, the decompression chamber is closed and evacuated to set a predetermined reduced pressure atmosphere in the decompression chamber. After the decompression chamber becomes a predetermined reduced pressure atmosphere, the cylinder is actuated to superimpose the two transparent substrates via the curable resin composition layer, and the curable resin composition is sealed in the space surrounded by the both transparent substrates and the sealing material to form a lamination precursor do. After forming the lamination precursor, the inside of the decompression chamber is returned to the atmospheric pressure atmosphere, and the lamination precursor is taken out from the decompression chamber.

The adhesion strength between the both transparent substrates and the sealing material may be such that the gas does not enter from the interface between the transparent substrate and the sealing material when the lamination precursor is placed under atmospheric pressure. For example, a pressure-sensitive adhesive layer may be formed on the surface of the sealing material so that the transparent substrate and the sealing material are in close contact with each other. If necessary, a curable adhesive may be formed on the interface between the transparent substrate and the sealing material, or a sealing material may be formed of a curable resin to form a lamination precursor, and then taken out from the decompression chamber or from the decompression chamber, Or the curable resin can be cured to increase the adhesion strength between the transparent substrate and the sealing material.

The second step is a step of curing the curable resin composition under atmospheric pressure of the lamination precursor. The curable resin composition of the present invention is a photocurable composition containing a photopolymerization initiator. The curable resin composition is photo-cured by irradiating light to the above-mentioned laminate precursor. Photocuring can be performed by irradiating light from a light source such as an ultraviolet lamp through a transparent substrate. As described above, it is preferable to maintain the lamination precursor under atmospheric pressure for a while and then cure the curable resin composition. By curing the curable resin composition, the curable resin composition becomes a cured resin, and a transparent laminate as described above is obtained.

Hereinafter, an example of a method for producing a transparent laminate according to the present invention will be described with reference to Fig.

In the first step, the sealing material 12 is formed over the entire periphery on the periphery of one transparent substrate 10 (hereinafter simply referred to as the "transparent substrate 10"), and the sealing material 12 is formed on the sealing material 12 The curable resin composition 14 is supplied to the surface of the transparent substrate 10 surrounded by the seal material 12 and the layer of the curable resin composition 14 is placed in the decompression chamber 26 horizontally. The other transparent substrate 16 (hereinafter simply referred to as &quot; transparent substrate 16 &quot;) is adsorbed to the invisible chamber 30, which can be moved up and down by the cylinder 34 in the decompression chamber 26 Is held by the pad 32, and is opposed in parallel above the transparent substrate 10. The decompression chamber 26 is closed and the vacuum pump 28 is operated to exhaust the inside of the decompression chamber 26 to a predetermined reduced pressure atmosphere. Thereafter, the cylinder 34 is operated to drop the transparent substrate 16, and the curable resin composition 14 is sandwiched by the transparent substrate 10 and the transparent substrate 16 with the curable resin composition 14 layer therebetween, A sealed precursor is formed by the transparent substrate 10, the transparent substrate 16, and the sealing material 12.

In the second step, the inside of the decompression chamber 26 is returned to the atmospheric pressure atmosphere, the lamination precursor is taken out from the decompression chamber 26, and the curable resin composition of the lamination precursor is cured by light irradiation in an atmospheric pressure atmosphere, I get a sieve.

Example

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

In addition, the hydroxyl value is a value determined by JIS K1557-1 (2007 edition).

[Preparation Example 1: Preparation of polyoxyalkylene polyol]

A reaction vessel equipped with a stirrer and a nitrogen inlet tube was used and the reaction was carried out while slowly adding propylene oxide to the initiator propylene glycol at 130 占 폚 under a nitrogen atmosphere to prepare a catalyst After deactivation, potassium hydroxide was used as a catalyst, and then ethylene oxide was reacted. The product was withdrawn from the reaction vessel to obtain a polyoxyalkylene polyol. The obtained polyoxyalkylene polyol was poly (oxypropylene.oxyethylene) diol having an average number of hydroxyl groups of 2, a hydroxyl value of 28.7 mgKOH / g, and an oxyethylene group content of 24 mass%.

[Example 1]

460.3 g of poly (oxypropylene.oxyethylene) diol obtained in Production Example 1 as polyol and 32.9 g of isophorone diisocyanate (hereinafter referred to as IPDI) were added to a reaction vessel equipped with a stirrer and a nitrogen introduction tube, 0.039 g of dioctyltin distearate (hereinafter referred to as DOTDS) was further added and reacted at 70 DEG C for 10 hours to obtain an isocyanate-terminated urethane prepolymer (INDEX = 1.22).

Subsequently, 0.135 g of dibutyltin dilaurate (hereinafter referred to as DBTDL) and 0.15 g of 2,5-di-tert-butylhydroquinone (hereinafter referred to as DtBHQ) were added to the urethane prepolymer of the isocyanate- g, 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was added, and the content of the isocyanate group was measured by NCO titration according to JIS K1603-1, and the reaction was repeated until the isocyanate group disappeared To obtain an unsaturated urethane acrylate oligomer. Hereinafter, the obtained unsaturated urethane acrylate oligomer is referred to as oligomer (A1).

30 g of the obtained oligomer (A1), 30 g of 4-hydroxybutyl acrylate (hereinafter referred to as 4HBA), 30 g of lauryl acrylate (hereinafter referred to as LA) 3 g of Rocicyclohexyl phenyl ketone (hereinafter referred to as HCHPK), 0.3 g of IRGANOX-1010 (manufactured by BASF) as antioxidant, 0.04 g of DtBHQ as a polymerization inhibitor, and 1-decane 0.8 g of thiol was added and mixed to prepare a curable resin composition.

[Examples 2 to 9, Comparative Examples 1 to 3]

The curable resin compositions of Examples 2 to 9 and Comparative Examples 1 to 3 were prepared by changing the thiol compound (D) and the addition amount of the thiol compound of Example 1 to those shown in Tables 2 to 4.

In the tables, "thiocarco" is a trade name of 1-dodecanethiol, and "car lens PE-1" is a trade name of pentaerythritol tetrakis (3-mercaptobutyrate).

[evaluation]

(Storage elastic modulus)

The curable resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 3 were measured for storage elastic modulus (G ') after 1 minute of curing with a HgXe (100 mW / cm2) lamp using a rheometer MCR-301 manufactured by Antonpaar Respectively. The measurement conditions were a sample thickness of 0.4 mm, a frequency of 1 Hz, a strain of 1%, and a temperature of 35 캜.

(Storage stability)

About 80 ml of each of the photocurable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was placed in a 100 ml brown vial bottle and stored in an oven at 85 ° C for 1 day and 2 days. The storage modulus (G ' And the change in elastic modulus from storage elastic modulus before storage was analyzed.

(%) Of the storage elastic modulus (G ') = [(G' after oven storage at 85 ° C - initial G ') / initial G'] × 100

A change rate of the storage elastic modulus (G ') after 2 days was 30% or less.?, 30% or more and 50% or less?, 50% or more and 80% or more.

(stink)

The odor of the photocurable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated as odor by two evaluators and odorless by O evaluators.

[result]

As shown in Tables 2 to 4, the addition of the thiol compound (D) described in the Examples gave a curable resin composition excellent in both storage stability and odor as compared with Comparative Examples. Comparative Example 1 in which the thiol compound (D) was not added had poor storage stability. Comparative Example 2 in which the molecular weight per SH group is out of the range of the present invention and Comparative Example 3 in which the number of carbon atoms per SH group is outside the range of the present invention was able to lower initial storage modulus (G '), but storage stability was poor.

Industrial availability

The curable resin composition of the present invention is useful as a raw material for an adhesive resin layer of a laminated glass and is useful as a transparent laminate of the present invention, a laminated glass (windshield glass, safety glass, security glass, etc.) Do.

The specification, claims, abstract and drawings of Japanese Patent Application No. 2012-162536 filed on July 23, 2012 are incorporated herein by reference in their entirety and are hereby incorporated herein by reference.

10, 16 ... Transparent substrate,
12 ... Sealing material,
14 ... Curable resin composition,
26 ... Decompression chamber,
28 ... Vacuum pump,
30 ... However,
32 ... Absorption pad,
34 ... cylinder,
36 ... UV curable resin for sealing.

Claims (14)

A curable resin composition comprising a urethane oligomer (A), a compound (B) having one of the following curable functional groups and one hydroxyl group, the following thiol compound (D), and a photopolymerization initiator.
The curable functional _{group: CH 2 = C (R)} C (O) group represented by O- (where, R represents a hydrogen atom or a methyl group).
Unsaturated urethane oligomer (A): an unsaturated urethane oligomer obtained by reacting a polyoxyalkylene polyol (a1), a polyisocyanate (a2) and a compound (a3) having a curing functional group and a hydroxyl group in the presence of an organotin compound, An unsaturated urethane oligomer obtained by reacting an oxyalkylene polyol (a1) and a compound (a4) having the curable functional group and an isocyanate group in the presence of an organotin compound.
Thiol compound (D): a primary thiol compound (D1) having a molecular weight of 70 to 420 per one-SH group or a secondary thiol compound (D2) having a molecular weight of 28 to 420 per one-SH group. The method according to claim 1,
Wherein the curable functional group is an acryloyloxy group. 3. The method according to claim 1 or 2,
The unsaturated urethane oligomer (A) has an average of 2 to 3 curable functional groups per molecule. 4. The method according to any one of claims 1 to 3,
Wherein the polyoxyalkylene polyol (a1) is a poly (oxypropylene.oxyethylene) polyol having an average number of hydroxyl groups of 2 to 3, a hydroxyl value of 15 to 30 mgKOH / g and an oxyethylene group content of 8 to 50 mass% Resin composition. 5. The method according to any one of claims 1 to 4,
Wherein the polyisocyanate (a2) is an alicyclic diisocyanate or an aliphatic diisocyanate. 6. The method according to any one of claims 1 to 5,
Wherein the compound (a3) is a hydroxyalkyl acrylate having a hydroxyalkyl of 2 to 12 carbon atoms. 7. The method according to any one of claims 1 to 6,
Wherein the organic tin compound is an organic tin carboxylic acid ester. 8. The method according to any one of claims 1 to 7,
Wherein the compound (B) is a monohydroxyalkyl acrylate having a hydroxyalkyl having 3 to 8 carbon atoms. 9. The method according to any one of claims 1 to 8,
Wherein the thiol compound (D1) is an aliphatic thiol compound. 9. The method according to any one of claims 1 to 8,
Wherein the thiol compound (D2) is an aliphatic thiol compound having 3 to 40 carbon atoms or an alicyclic thiol compound having 3 to 40 carbon atoms. 11. The method according to any one of claims 1 to 10,
Further, the curable resin composition contains one compound having the above-mentioned curable functional group and the compound (C) having an alkyl group having 8 to 22 carbon atoms. 12. The method according to any one of claims 1 to 11,
Wherein the curable resin composition contains 20 to 75 mass% of the unsaturated urethane oligomer (A), 10 to 50 mass% of the compound (B), and 0.05 to 3.0 mass% of the thiol compound (D). A transparent laminate having a pair of transparent substrates and a cured resin layer interposed between the transparent substrates,
Wherein the cured resin is a cured product of the curable resin composition according to any one of claims 1 to 12. A curable resin composition according to any one of claims 1 to 12, wherein the curable resin composition layer is formed on one transparent substrate and another transparent substrate is superimposed on the curable resin composition layer in a reduced pressure atmosphere, A first step of producing a lamination precursor having the curable resin composition sealed between a substrate and a pair of transparent substrates,
And a second step of curing the curable resin composition under an atmosphere in which the lamination precursor is placed in an atmosphere having a higher pressure than the pressure-reduced atmosphere.

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