KR20170031759A - Curable resin composition - Google Patents

Abstract

The curable resin composition contains (A) a thioether-containing (meth) acrylate derivative having a specific structure and (B) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 50,000. (A) / (B) of the component (A) and the component (B) is 0.05 to 30.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition capable of obtaining a cured film excellent in adhesion and flexibility to a substrate even in cold regions.

BACKGROUND ART Conventionally, there is a technique of adding a silane coupling agent in order to improve adhesion to an inorganic substrate such as a paint containing an epoxy resin as a main component (JP-A-7-300491). However, a considerable number of silane coupling agents have a low boiling point, and therefore it has been necessary to add a large amount of the silane coupling agent to the thermosetting resin. In addition, the effect of improving the adhesion by the addition of the silane coupling agent is not sufficient. For example, by adding a salt such as titanium · zirconium or an adhesion auxiliary such as phosphate ester or urethane resin at the same time, There are many cases that can be done. In this case, there is a problem that the addition of these adhesion adjuvants not only increases the number of steps, but also requires selection of the adhesion adjuvant species that does not impair the paint properties and a strict optimization of the addition amount.

Japanese Laid-Open Patent Publication No. 2012-246464 discloses a curable resin composition obtained by mixing a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds. As in the case of using a silane coupling agent, this curable resin composition does not need to be added with any other adhesion promoter or the like, and can exert excellent adhesion to an inorganic substrate.

However, a curable resin composition obtained by mixing a polyfunctional thiol compound and a specific thioether-containing alkoxysilane derivative with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds, as in JP-A-2012-246464, And the storage stability of the resin composition is excellent. However, it has been found that there is a problem that cracks tend to occur at the time of bending of the cured film, and the adhesion is insufficient, because the cured film has insufficient flexibility in cold regions.

For this reason, there is a demand for a material which is excellent in adhesion to a base material even in cold regions and has flexibility of the obtained cured film.

(Meth) acrylate derivative represented by the following formula (1), (B) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 50,000, and (A) / (B)) of the component (A) and the component (B) is 0.05 to 30.

[Chemical Formula 1]

(Wherein a is an integer of 1 to 2, b is an integer of 1 to 2, and a + b = 3. R ¹ is a trivalent group represented by the following formula 2 and R ² is a group represented by the following formula 3 or 4, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms.)

(2)

(Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH (CH ₃ ) -)

(3)

(R < ⁵ > is a hydrogen atom or a methyl group)

[Chemical Formula 4]

(R < ⁵ > is a hydrogen atom or a methyl group)

In another aspect of the present disclosure, the curable resin composition may further contain (C) a photopolymerization initiator in addition to the above components (A) to (B). The component (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B).

In another aspect of the disclosure, the curable resin composition may further comprise (D) an amine compound having a weight average molecular weight of 90 to 700 in addition to the components (A) to (B) . The component (D) is 0.01 to 50 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B).

According to the curable resin composition, the multifunctional (meth) acrylate (B) having a specific molecular weight is well balanced with the specific thioether-containing (meth) acrylate derivative (A) serving as an effective component for improving the adhesion property . Thereby, as in the case of using a conventional silane coupling agent, the cured film of the curable resin composition can achieve excellent adhesion to the substrate without adding any other adhesion promoter or the like. Particularly, even in a cold region, the obtained cured film exerts excellent adhesion and flexibility to a substrate.

The curable resin composition of the present disclosure contains the following components (A) and (B) as essential components, optionally further containing at least one of components (C) and (D) In the present disclosure, "molecular weight" means "weight average molecular weight" unless otherwise specified. The term "(meth) acrylate" means a generic term including both acrylate and methacrylate, and the term "(meth) acryloxy group" means a generic term including both an acryloxy group and a methacryloxy group. The description of " xx to xx " indicating the numerical value range includes the lower limit value (xx) and the upper limit value (xx), that is, &Quot;

<Thioether-containing (meth) acrylate derivative (component (A))>

The thioether-containing (meth) acrylate derivative as the component (A) is a compound represented by the following formula (1).

[Chemical Formula 5]

(Wherein a is an integer of 1 to 2, b is an integer of 1 to 2, and a + b = 3. R ¹ is a trivalent group represented by the following formula 2 and R ² is a group represented by the following formula 3 or 4, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms.)

[Chemical Formula 6]

(Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH (CH ₃ ) -)

(7)

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)

[Chemical Formula 8]

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R &lt; ³ &gt; in the formula (1) include a linear alkyl group, an alkyl group having a side chain, and a cyclic alkyl group.

R ⁴ in the above-mentioned formula (2) is preferably a methylene group, an ethylene group or an isopropylene group, and an ethylene group or an isopropylene group is particularly preferable in that the adhesion improving property is enhanced.

<Multifunctional (meth) acrylate (Component (B))>

The polyfunctional (meth) acrylate as the component (B) has a (meth) acryloxy group at the terminal, and as a preferable example thereof, a compound represented by the following formula (5) can be given. The polyfunctional (meth) acrylate as the component (B) may be used alone or in combination of two or more.

[Chemical Formula 9]

(Wherein C is an integer of 2 to 30, and R ⁶ is a hydrocarbon group having 2 to 200 carbon atoms, ether oxygen (-O-) having 2 to 300 carbon atoms and a hydrocarbon group alone, or an isocyanurate ring or iso A cyano group and a hydrocarbon group, and R &lt; ⁷ &gt; is a hydrogen atom or a methyl group)

As the polyfunctional (meth) acrylate (B), a polymer type may also be preferably used. Examples of the polymer type polyfunctional (meth) acrylate include (meth) acrylates having epoxy groups such as glycidyl (meth) acrylate or the like having a group reacting with an epoxy group such as (meth) (Meth) acrylate, a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, or a copolymer obtained by reacting with a hydroxyl group such as 2-methylpropene 2-isocyanatoethyl (Meth) acrylate having a group capable of reacting with a carboxyl group such as glycidyl (meth) acrylate on a (meth) acrylate having a carboxyl group such as (meth) acrylic acid or the like, (Meth) acrylate, and the like.

The weight average molecular weight of the polyfunctional (meth) acrylate (B) is 200 to 50000, preferably 220 to 40000, and more preferably 240 to 30000. Even if the weight average molecular weight of the polyfunctional (meth) acrylate (B) is less than 200, there is no problem with the adhesion, but the volatility increases and the odor tends to become strong. On the other hand, when the weight average molecular weight is more than 50,000, the adhesion is not a problem, but the solubility in other components may be lowered.

The (meth) acrylate equivalent of the polyfunctional (meth) acrylate (B) is 80 to 6000 g / mol, preferably 80 to 4500 g / mol, more preferably 85 to 3000 g / mol. If the (meth) acrylate equivalent is less than 80 g / mol, the (meth) acryloxy group per unit volume becomes excessive, so that (A) the thiol group of the thioether-containing (meth) If a large amount remains, the toughness of the cured film composed of the curable resin composition may decrease, and the adhesion may deteriorate. On the other hand, when the (meth) acrylate equivalent is more than 6000 g / mol, the reaction efficiency with the thiol group of the thioether-containing (meth) acrylate derivative is lowered because (A) the (meth) The toughness of the cured film made of the curable resin composition may decrease, and the adhesion may be lowered.

&Lt; Photopolymerization initiator (Component (C)) &gt;

The photopolymerization initiator as the component (C) is added in order to accelerate the reaction between the thiol group and the (meth) acryloxy group, and light irradiation required for curing of the curable composition can be reduced. Examples of the photopolymerization initiator include photo radical polymerization initiators, photocathion polymerization initiators, and photoanionic polymerization initiators. The photocatalytic polymerization initiator is preferably used for shortening the reaction time, and the photocathon polymerization initiator is preferably used when the curing shrinkage is reduced, and the photocatalytic polymerization initiator is used in the fields of electronic circuits and the like It is preferable to use it when imparting adhesiveness to the substrate.

Examples of the photo radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl-ketone, 2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-phenyl- Methyl-1- [4- (methylthio) -2-methyl-propan-1- Phenyl] -2-morpholinopropane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide have.

Examples of the photocathione polymerization initiator include bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, Diphenyl iodonium hexafluoroarsenate, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) - hexafluoroarsenate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, 1,3,5-triazine, triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, etc. .

Examples of photoanionic polymerization initiators include, for example, acetophenone o-benzoyloxime, nifedipine, 2- (9-oxo xanthene-2-yl) propionic acid 1,5,7-triazabicyclo [ 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] (3-benzoylphenyl) propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidate, n-butyltriphenylborate and the like.

&Lt; Amine compound (Component (D)) &gt;

The amine compound (D) is added to accelerate (catalyze) the reaction between the thiol group and the (meth) acryloxy group. Specifically, by containing the component (D), the thiol group and the (meth) acryloxy group can be reacted at a low temperature, so that the curable resin composition comprising the component (A) and the component (B) can be cured at a low temperature. The amine compound as the component (D) includes a monofunctional amine having a weight average molecular weight of 90 to 700, preferably 100 to 690, and more preferably 110 to 680, and a polyamine having a plurality of amino groups. When the weight average molecular weight of the amine compound is less than 90, the volatility of the amine increases, which causes bad odor and voids. In addition, since the amine concentration at the time of heat curing is low, the crosslinking reaction is difficult to proceed and adhesion tends to decrease. When the weight average molecular weight of the amine compound is more than 700, the water resistance is lowered and the adhesiveness is likely to be lowered.

Monofunctional amines include primary amines, secondary amines, and tertiary amines. The polyamines include primary amines, secondary amines, tertiary amines, and complex amines. The complex amine is an amine having at least two of a primary amino group, a secondary amino group and a tertiary amino group. Such complex amines include imidazoline compounds, imidazole compounds, N-substituted piperazine compounds, N, N-dimethylurea derivatives and the like. In addition, the amine compound may be used alone or in admixture of two or more.

The amine compound may form a salt with an organic acid in advance to adjust the catalytic activity. Examples of the organic acid to be reacted with the amine compound in advance include aliphatic carboxylic acids such as stearic acid and 2-ethylhexanoic acid having 1 to 20 carbon atoms and 1 to 5 carboxyl groups, 1 to 20 carbon atoms, Aromatic carboxylic acids such as pyromellitic acid, trimellitic acid and benzoic acid having 10 carbon atoms, or isocyanuric acid.

Of the amine compounds, an imidazole compound having a high basicity is suitable for curing at the lowest temperature. An imidazole compound coated with a phenol resin or the like can also be used.

This imidazole compound is a compound represented by the following formula (6).

[Chemical formula 10]

(R ⁹ is a cyano group, an alkoxy group, or a hydrogen atom of a hydrocarbon group having 1 to 10 hydrocarbon group, a 2,3-diamino-tree of 1 to 10 carbon atoms substituted with a triazine, having a carbon number of 1 to 4, R ^8, R ¹⁰ and R ¹¹ are a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, and a hydrocarbon group having 2 to 8 carbon atoms when R ⁸ to R ¹¹ are combined to form a ring )

Specific examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) Imidazole, 1- (2-cyanoethyl) -2-undecylimidazole, 1- (2-cyanoethyl) Ethyl-4-methylimidazole, 2,3-dihydro-lH-pyrrolo [1,2-a] benzimidazole, 2,4-diamino-6- [2-methylimidazolyl- (1)] ethyl-s-triazine, 2,4-diamino- 1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

<Composition ratio (compounding balance)>

The curable resin composition is formulated such that the mass ratio (A) / (B) of the (A) thioether-containing (meth) acrylate derivative and the (B) polyfunctional (meth) acrylate is 0.05 to 30. Here, "(A) / (B)" is a value obtained by dividing the mass of the (A) thioether-containing (meth) acrylate derivative by the mass of the (B) polyfunctional (meth) acrylate. When the ratio (A) / (B) is less than 0.05 or more than 30, the adhesion tends to decrease. The optimum value of (A) / (B) depends on the properties required of the curable resin composition, and depending on the kind of the (A) thioether-containing (meth) acrylate derivative and (B) the polyfunctional (meth) Do. The properties of the curable resin composition after curing are strictly influenced by the value of (thiol group number) / ((meth) acryloxy group number) (hereinafter referred to as thiol / environ) in the unit weight of the curable resin composition. For example, when the thiol / ene ratio is in the range of 0.5 to 1.5, it is easy to form a dense cross-linking and tends to be a hard cured product. On the other hand, when the thiol / ene ratio is 0.1 or more and less than 0.5 or more than 1.5 and 2.0 or less, a flexible and adhesive cured product can be obtained. If the thiol / ene ratio is less than 0.1 or more than 2.0, gelation becomes difficult and adhesion tends to decrease.

The curable resin composition is prepared by mixing (C) 100 parts by mass of the total mass of the (A) thioether-containing (meth) acrylate derivative and (B) the polyfunctional (meth) And the photopolymerization initiator is added in an amount of 0.01 to 10 parts by mass. When the amount of the component (C) is less than 0.01 part by mass based on 100 parts by mass of (A) + (B), a large amount of accumulated light is required for the reaction between the thiol group and the (meth) acryloxy group to proceed, When the amount exceeds the above-mentioned range, the crosslinking density is lowered and the adhesion may be lowered.

When the amine compound (D) is also added to the curable resin composition, the total weight of the (A) + (meth) acrylate derivative of the (A) thioether- (D) is added in an amount of 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass, based on 100 parts by mass of the component (B)). If the amount of the component (D) is less than 0.01 based on the amount of the component (A) + (B), the function as a catalyst becomes insufficient and does not promote the curing by heating. When the amount exceeds 50 parts by mass, .

&Lt; Formation of cured film &

The curable resin composition can be coated on a substrate and cured to form a cured film. The curable resin composition exhibits adhesion to a substrate due to the thioether group of the (A) thioether-containing (meth) acrylate derivative. Therefore, examples of the substrate include inorganic substrates such as a transition metal or an alloy thereof, a silicon compound, a phosphorus compound, a sulfur compound, or a boron compound that forms a chemical bond with a thioether group (having a high chemical affinity) An organic substance having an unsaturated bond (including an aromatic ring), an organic substance having a hydroxyl group or a carboxyl group, or an organic substance treated with plasma or UV ozone. Specifically, examples of the inorganic substrate include glass, silicon, various metals, and the like. Examples of the organic base material include poly (meth) acrylic resins, triacetate cellulose (TAC) resins, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate, polycarbonate resins, polyimide resins, Polyolefin resin such as polypropylene, polycarbonate, polyimide, ABS resin, polyvinyl alcohol, vinyl chloride resin, polyacetal and the like are preferable. In the curable resin composition, (A) the thioether-containing (meth) acrylate derivative has a specific hydrocarbon group, whereby the cured film is excellent in flexibility. Therefore, even under a cold condition, the cured film is easy to follow the substrate, and the adhesion to the substrate is excellent. Therefore, it can be particularly preferably used for coating of a flexible substrate which can be used particularly under cold conditions.

The curable resin composition can be cured by irradiating light. Examples of light to be irradiated include active energy rays such as UV (ultraviolet rays) and EB (electron beams). When the curable resin composition contains the component (C), it is possible to reduce the light irradiation amount required to about 2500 mJ / cm 2 to about 100 mJ / cm 2. When the curable resin composition contains the component (D), curing at a low temperature of about 80 캜 is possible. When the curable resin composition contains the component (C) and the component (D), the curable resin composition may be cured through a two-step process of a curing process by light irradiation and a curing process by heating.

The curable resin composition may be used by diluting with an organic solvent in order to uniformize the reaction system and to facilitate the coating. Examples of such organic solvents include alcohol solvents, aromatic hydrocarbon solvents, ether solvents, ester solvents and ether ester solvents, ketone solvents and phosphate ester solvents. These organic solvents are preferably suppressed to a blending amount of less than 10000 parts by mass based on 100 parts by mass of the curable resin composition. Basically, since the solvent is volatilized at the time of becoming a cured film, the physical properties of the cured film are not greatly affected.

The curable resin composition may contain a viscosity adjusting agent such as silica powder for the purpose of adjusting the viscosity. It is preferable that these viscosity modifiers are controlled to a blending amount of less than 300 parts by mass based on 100 parts by mass of the curable resin composition. If the blending amount of the viscosity adjusting agent exceeds 300 parts by mass, the adhesion may possibly decrease.

The curable resin composition may be added with various additives used for ordinary paints and adhesives. Examples of such additives include a surfactant for smoothing the coated surface, and an aluminum salt for prolonging the usable time. These additives are preferably suppressed to a blending amount of less than 80 parts by mass with respect to 100 parts by mass of the curable resin composition. When the blending amount of these additives exceeds 80 parts by mass, there is a possibility that the adhesiveness is lowered.

Example

Next, the curable resin composition will be described in more detail with reference to Examples and Comparative Examples. The components used in this example and the comparative example are as follows. Mw represents the weight average molecular weight.

&Lt; Component (A) &gt;

(A-1: thioether-containing (meth) acrylate derivative)

(11)

(A-2: thioether-containing (meth) acrylate derivative)

[Chemical Formula 12]

(A-3: thioether-containing (meth) acrylate derivative)

[Chemical Formula 13]

(A-4: thioether-containing (meth) acrylate derivative)

[Chemical Formula 14]

(A-5: thioether-containing (meth) acrylate derivative)

[Chemical Formula 15]

(A-6: polyhydric thiol compound)

[Chemical Formula 16]

(A-7: polyvalent thiol compound)

[Chemical Formula 17]

(A-8: thioether-containing alkoxysilane derivative)

[Chemical Formula 18]

(A-9: thioether-containing alkoxysilane derivative)

[Chemical Formula 19]

(A-10: thioether-containing (meth) acrylate derivative)

[Chemical Formula 20]

&Lt; Component (B): polyfunctional (meth) acrylate &gt;

(B-1, Mw: 5000)

[Chemical Formula 21]

(n is an average of 13)

(B-2, Mw: 246)

[Chemical Formula 22]

(B-3, Mw: 352)

(23)

(B-4, Mw: 22000)

A polymer (50 wt% methyl isobutyl ketone solution, reprecipitated with hexane as a 50 wt% solution of methyl isobutyl ketone) was added to the copolymer of glycidyl methacrylate and cyclohexyl methacrylate as a catalyst of the following D- .

(B-5, Mw: 45000)

A polymer (50 wt% methyl isobutyl ketone solution, reprecipitated with hexane as a 50 wt% solution of methyl isobutyl ketone) was added to the copolymer of glycidyl methacrylate and cyclohexyl methacrylate as a catalyst of the following D- .

&Lt; Component (C): Photopolymerization initiator &gt;

(C-1, Mw: 204)

1-Hydroxy-cyclohexyl-phenyl-ketone

(C-2, Mw: 348)

2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

(C-3, Mw: 407)

2- (9-oxo-xanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] deca-

&Lt; Component (D): amine compound &gt;

(D-1, Mw: 110)

&Lt; EMI ID =

(D-2, Mw: 102)

N, N-dimethyl-1,3-propanediamine

(D-3, Mw: 680)

(25)

(n1, n2, n3 are integers of 1 to 5, and the average is 3.5)

The components (A) to (D) were each mixed at the mixing ratios shown in Tables 1 to 4 and stirred until uniform with a spatula to obtain samples of the curable resin compositions of Examples and Comparative Examples. The samples of each of the curable resin compositions of the obtained examples and comparative examples were evaluated for adhesion 1 (room temperature adhesion), adhesion 2 (cold weather adhesion), flexibility and storage stability. The results are shown in Tables 1 to 4.

[Preparation of test piece for evaluation]

Adhesion 1, Adhesion 2, and a test piece for evaluation of flexibility were obtained as follows. Each sample of the curable resin composition was coated on a PET film having a width of 25 mm at a thickness of 100 microns by a die coater and then a separate PET film was laminated thereon and cured under the curing conditions shown in Tables 1 to 4 . As the PET film, Lumirror U46-100 manufactured by Toray Industries, Inc. was used. For light irradiation, a UV lamp system "Light Hammer 6" manufactured by Heraus Noble Light Fusion Inc. was used, and a bulb H was used as the lamp bulb.

[Adhesiveness 1 (Adhesion at room temperature)]

The test piece for evaluation was allowed to stand still at 25 占 폚 for 24 hours and then measured by the T-type peeling method prescribed in JIS K6854-3 within 5 minutes and evaluated as follows.

⊚: tensile strength of 5 N / 25 mm or more (breakage of PET film)

?: Tensile strength of 5 N / 25 mm or more (PET film is not broken)

X: less than 5 N / 25 mm

[Adhesiveness 2 (Adhesion of Cold Paper)]

The evaluation test piece was allowed to stand still at -10 deg. C for 24 hours and then measured by the T-type peeling method defined in JIS K6854-3 within 5 minutes and evaluated as follows.

⊚: tensile strength of 5 N / 25 mm or more (breakage of PET film)

?: Tensile strength of 5 N / 25 mm or more (PET film is not broken)

X: less than 5 N / 25 mm

[flexibility]

The test piece for evaluation was allowed to stand at -10 占 폚 for 24 hours, and then wound within a period of 5 minutes in a rod having a diameter of 8 mm for 1 minute and observed with naked eyes.

○: 0 cracks

X: 1 or more cracks

[Storage stability]

The viscosity of the curable resin composition sample of each of the examples and comparative examples was measured immediately after mixing (viscosity immediately after mixing) at 25 ° C, and after heating at 40 ° C for 12 hours, the viscosity (viscosity after heating ) Was measured, and the viscosity after heating was divided by the viscosity immediately after mixing to calculate the increasing ratio, and the evaluation was made as follows. The viscosity was measured using an R-type viscometer manufactured by Toray Industries, Ltd. under the following conditions.

Used rotor: 1 ° 34 '× R24

Measuring range: 0.5183 ~ 103.7 Pa · s

◎: Increase ratio 1.0 to 1.8

○: Increase ratio 1.8 to 10

×: Increase ratio Out of the above range

The curable resin compositions of Examples 1-1 to 1-13 were confirmed to have high adhesiveness under room temperature and cold conditions, good flexibility, and excellent storage stability. The curable compositions of Examples 2-1 to 2-5 were cured by irradiation of a small amount of light and confirmed high adhesiveness, good flexibility, and excellent storage stability under room temperature and cold conditions. The curable compositions of Examples 3-1 to 3-5 were cured by a small amount of light irradiation and low-temperature heating, and high adhesiveness, good flexibility, and excellent storage stability under room temperature and cold conditions were confirmed. On the other hand, in Comparative Example 1-2, in which the component (A) is too large relative to the components of Comparative Example 1-1 and Component (B) in which the component (A) Was inferior. In Comparative Examples 1-3 to 1-7 in which the compound having no structure of the formula 1 was used as the component (A), the adhesiveness under a cold condition was inferior.

Claims (3)

(A) a thioether-containing (meth) acrylate derivative represented by the following formula (1)
(B) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 50000,
Wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 0.05 to 30.
[Chemical Formula 1]

(Wherein a is an integer of 1 to 2, b is an integer of 1 to 2, and a + b = 3. R ¹ is a trivalent group represented by the following formula 2 and R ² is a group represented by the following formula 3 or 4, and R ³ is a hydrocarbon group having 1 to 12 carbon atoms.)
(2)

(Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH (CH ₃ ) -)
(3)

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group)
[Chemical Formula 4]

(R &lt; ⁵ &gt; is a hydrogen atom or a methyl group) The method according to claim 1,
(C) a photopolymerization initiator in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B). 3. The method according to claim 1 or 2,
(D) a curing resin composition containing an amine compound having a weight average molecular weight of 90 to 700 in an amount of 0.01 to 50 parts by mass based on 100 parts by mass of the total mass of the component (A) and the component (B).