TW201725231A - Curable resin composition - Google Patents

Abstract

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

Description

Curable resin composition

The present invention relates to a curable resin composition which is excellent in adhesion to a substrate even in a cold region and which is excellent in flexibility.

In the past, in order to improve the adhesion of a coating material containing an epoxy resin as a main component to an inorganic substrate, there is a technique of adding a decane coupling agent (JP-A No. 7-300491). However, the decane coupling agent mostly has a low boiling point and needs to be added in a large amount to the thermosetting resin. Further, the effect of improving the adhesion by the addition of the decane coupling agent is also insufficient, and it is possible to obtain a practical level by simultaneously adding a salt, a phosphate, a urethane resin or the like to a practical level. There are also many cases of attachment. At this time, the addition of these adhesion aids not only increases the number of processes, but also has problems such as the necessity of selecting the type of the adhesion aid which does not impair the coating property or the strict optimization operation of the addition amount thereof.

JP-A-2012-246464 discloses mixing a polyfunctional thiol compound and a specific thioether-containing alkoxydecane derivative with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds. Curable resin composition. The curable resin composition can exhibit excellent adhesion to an inorganic substrate as in the case of using a decane coupling agent without adding another adhesion aid.

[Problems to be solved by the invention]

However, it is clear that the polyfunctional thiol compound and the specific thioether-containing alkoxydecane derivative are mixed with an epoxy resin composition and a polyfunctional polyene having a plurality of double bonds, as disclosed in Japanese Laid-Open Patent Publication No. 2012-246464. The curable resin composition is excellent in adhesion to an inorganic substrate and excellent in stability of a resin composition, but has a technical problem that a cured film is likely to be cracked when bent in a cold region due to lack of flexibility ( Crack) and lack of attachment.

Therefore, there is a need for a material which is excellent in adhesion to a substrate even in a cold region and which has flexibility in the obtained cured film.

[Technical means to solve technical problems]

In one aspect of the invention, the curable resin composition contains (A) a thioether-containing (meth) acrylate derivative represented by the following formula 1, and (B) a polyfunctional weight having a weight average molecular weight of 200 to 50,000 (A) The base acrylate has a mass ratio ((A)/(B)) of (A)/(B) of 0.05 to 30.

In the formula, 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, R ² is a divalent group represented by the following formula 3 or the following formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms; Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group.

In another aspect of the invention, the curable resin composition may further contain (C) a photopolymerization initiator in addition to the 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 invention, the curable resin composition may further contain (D) an amine having a weight average molecular weight of 90 to 700 in addition to the components (A) to (B) or (A) to (C). Compound. 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).

[effect of the invention]

According to the curable resin composition of the present invention, a specific thioether-containing (meth) acrylate derivative (A) is used as an active ingredient for improving the adhesion, and a specific molecular weight is added in a well-balanced manner. Functional (meth) acrylate (B). Therefore, it is not necessary to add another adhesion aid or the like as in the conventional decane coupling agent, and the cured film of the curable resin composition can also have excellent adhesion to the substrate. In particular, even in a cold region, the obtained cured film exhibits excellent adhesion to a substrate and flexibility.

The curable resin composition of the present invention contains the following components (A) and (B) as essential components, and further optionally contains at least one of the components (C) and (D). Further, in the present invention, the "molecular weight" means the weight average molecular weight unless otherwise specified. "(Meth)acrylate" is a generic term including both acrylate and methacrylate, and "(meth)acryloxy" is a generic term including propylene methoxy and (meth) propylene oxy. Unless otherwise stated, "○○~××" indicating the numerical range includes the upper limit value ("○○") and the lower limit value ("××"), that is, correctly, it means "○○ or more" ××以下”.

<Sulfur ether-containing (meth) acrylate derivative ((A) component)>

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

In the formula, 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, R ² is a divalent group represented by the following formula 3 or the following formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms; Wherein R ⁴ is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group, R ⁵ is a hydrogen atom or a methyl group.

The hydrocarbon group having 1 to 12 carbon atoms of R ³ in the above formula 1 may, for example, be a linear alkyl group, an alkyl group having a side chain or a cycloalkyl group.

R ⁴ in the above formula 2 is a methylene group, an ethylene group or an isopropylidene group which are the same as each other, and an ethylene group and an isopropylidene group are particularly preferable because of an effect of improving the adhesion.

<Polyfunctional (meth) acrylate ((B) component)>

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

In the formula, c is an integer of 2 to 30, R ⁶ is a hydrocarbon group having 2 to 200 carbon atoms, a group having 2 to 300 carbon atoms and only a group consisting of ether oxygen (-O-) and a hydrocarbon group, or An isocyanurate ring or a group formed only of an isocyanurate ring and a hydrocarbon group, and R ⁷ is a hydrogen atom or a methyl group.

Further, as the (B) polyfunctional (meth) acrylate, a polymer type can also be suitably used. Examples of the polymer-type polyfunctional (meth) acrylate include a (meth) acrylate having a group reactive with an epoxy group such as (meth)acrylic acid, and (meth) a polymer obtained by reacting a homopolymer or a copolymer of an epoxy group-containing (meth) acrylate such as glycidyl acrylate; for example, 2-isocyanoethyl 2-methacrylate or the like a polymer obtained by reacting a (meth) acrylate of a group reactive with a hydroxyl group with a homopolymer or copolymer of a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth)acrylate; A (meth) acrylate having a group reactive with a carboxyl group such as glycidyl methacrylate is reacted with a homopolymer or a copolymer of a (meth) acrylate having a carboxyl group such as (meth)acrylic acid. The obtained polymer or the like.

(B) The polyfunctional (meth) acrylate has a weight average molecular weight of from 200 to 50,000, preferably from 220 to 40,000, more preferably from 240 to 30,000. (B) When the weight average molecular weight of the polyfunctional (meth) acrylate is less than 200, there is no problem concerning adhesion, but the volatility tends to increase and the odor tends to be strong, which is not preferable. On the other hand, when the weight average molecular weight is more than 50,000, there is no problem concerning adhesion, but there is a possibility that the solubility of other components is lowered, which is not preferable.

Further, the (meth) acrylate equivalent of the (B) polyfunctional (meth) acrylate is 80 to 6000 g/mol, preferably 80 to 4,500 g/mol, more preferably 85 to 3,000 g/mol. If the (meth) acrylate equivalent is less than 80 g/mol, the thiol group of the (meth) acrylate-containing (meth) acrylate derivative is not present due to excess (meth) propylene oxime per unit volume. Since the (meth) propylene oxime group of the reaction remains in a large amount, the toughness of the cured film formed of the curable resin composition may be lowered, and the adhesion may be lowered. On the other hand, if the (meth) acrylate equivalent is more than 6000 g/mol, the (meth) propylene oxime group is significantly lower in concentration, and (A) the thioether-containing (meth) acrylate derivative thiol Since the reaction efficiency of the base is lowered, the toughness of the cured film formed of the curable resin composition may be lowered, and the adhesion may be lowered.

<Photopolymerization initiator ((C) component)>

In order to promote the reaction of the thiol group and the (meth) propylene oxime group, the photopolymerization initiator of the component (C) is added, and the light irradiation required for curing of the curable composition can be reduced. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanion polymerization initiator, and the like. The photopolymerization radical initiator is preferably used for shortening the reaction time, and the photocationic polymerization initiator is preferably used for reducing the curing shrinkage, and the photoanionic polymerization initiator is preferably used in a circuit or the like. The case of bonding in the field.

Examples of the photoradical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, and 2-hydroxyl group. -2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1- Ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, and the like.

Examples of the photocationic polymerization initiator include bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and cyclopropyl. Diphenylphosphonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, 2-(3,4-dimethoxystyryl)-4,6- Bis(trichloromethyl)-1,3,5-triazine, triphenylsulfonium tetrafluoroborate, triphenylphosphonium bromide, tri-p-tolylphosphonium hexafluorophosphate, tri-p-tolylphosphonium trifluoride Methanesulfonate and the like.

Examples of the photoanionic polymerization initiator include acetophenone-O-benzhydrazide, nifedipine, and 2-(9-oxanthon-2-yl)propionic acid 1,5,7-triaza. Bicyclo[4.4.0]non-5-ene, 2-nitrophenylmethyl 4-methylpropenyloxy acridine-1-carboxylate, 1,2-diisopropyl-3-[ Bis(dimethylamino)methylene]indole 2-(3-benzhydrylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5 tetramethylbisguanidinium butyl Triphenyl borate and the like.

<Amine compound ((D) component)>

The amine compound as the component (D) is added in order to promote (catalyze) a reaction between a thiol group and a (meth) acryloxy group. Specifically, since the thiol group and the (meth) propylene fluorenyl group can be reacted at a low temperature by containing the component (D), the curable resin containing the component (A) and the component (B) can be cooled at a low temperature. Cured. The amine compound as the component (D) may, for example, be a monofunctional amine having a weight average molecular weight of 90 to 700, preferably 100 to 690, more preferably 110 to 680, or 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 compound is increased, which causes not only the formation of odor and voids but also the decrease in the amine concentration at the time of heat curing, thereby causing the crosslinking reaction. It is difficult to carry out, and the adhesion is liable to decrease. When the weight average molecular weight of the amine compound exceeds 700, the water resistance is lowered, and the adhesion is liable to lower.

As the monofunctional amine, a primary amine, a secondary amine or a tertiary amine can be mentioned. Examples of the polyamine include a primary amine, a secondary amine, a tertiary amine, and a complex amine. The complex amine means two or more amines having a primary amino group, a secondary amino group, and a tertiary amino group. Examples of such a complex amine include an imidazoline compound, an imidazole compound, an N-substituted pyridazine compound, and an N,N-dimethylurea derivative. In addition, the amine compound may be used alone or in combination of two or more.

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

Among the amine compounds, the highly basic imidazole compound is most suitable for curing at a low temperature. Further, 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. (Formula 6)

R ⁹ is a cyano group, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms substituted by 2,3-diaminotriazine, an alkoxy group having 1 to 4 carbon atoms or hydrogen The atom, 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 R ⁸ to R ¹¹ are a carbon atom number 2 when bonded to form a ring. a hydrocarbon group of 8.

Specific examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, and 2-phenyl-4- Methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2- Methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2- Cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a] Benzimidazole, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-triazine, 2,4-diamino-6-[2-undecylimidazole -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-S Triazine, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole.

<composition ratio (equalization addition)>

The curable resin composition has a mass ratio ((A)/(B)) of (A) a thioether-containing (meth) acrylate derivative to (B) a polyfunctional (meth) acrylate of 0.05 to 30. Way to add. Here, "(A)/(B)" means a value obtained by dividing the mass of the (A) thioether-containing (meth) acrylate derivative by the mass of (B) the polyfunctional (meth) acrylate. When (A)/(B) is less than 0.05 or exceeds 30, there is a tendency that the adhesion is lowered. The optimum (A) / (B) value depends on the characteristics required for the curable resin composition, (A) a sulfide-containing (meth) acrylate derivative or (B) a polyfunctional (meth) acrylate. Different types. The properties after curing of the curable resin composition are strictly affected by the value of (number of thiol groups) / (number of (meth) propylene fluorenyl groups) (hereinafter referred to as thiol/olefin ratio) per unit weight of the curable resin composition. For example, if the thiol/ene ratio is in the range of 0.5 to 1.5, it is easy to form a close crosslink and it is easy to form a tough cured product. On the other hand, when the thiol/ene ratio is 0.1 or more and less than 0.5, or 2.0 or more and more than 1.5, a soft viscous cured product can be obtained. When the thiol/olefin ratio is less than 0.1 or exceeds 2.0, gelation is difficult, and the adhesion tends to be lowered.

Further, the curable resin composition has a total mass ((A) + (B)) 100 mass with respect to (A) a thioether-containing (meth) acrylate derivative and (B) a polyfunctional (meth) acrylate. A 0.01 to 10 parts by mass (C) photopolymerization initiator is added in portions. When the amount of the component (C) is less than 0.01 parts by mass based on 100 parts by mass of ((A) + (B)), a large amount of accumulated light is required, and a thiol group and a (meth) propylene fluorenyl group are performed. When the reaction exceeds 10 parts by mass, the crosslinking density may decrease and the adhesion may decrease.

Further, in the case where (D) an amine compound is added to the curable resin composition, (A) a sulfide-containing (meth) acrylate derivative and (B) a polyfunctional (meth) acrylate The total mass ((A) + (B)) is 100 parts by mass, and 0.01 to 50 parts by mass, preferably 0.01 to 45 parts by mass (D) of an amine compound is added. When the amount of the component (D) is less than 0.01 ((A)+(B))), the function as a catalyst is insufficient, and the curing promotion by heating is not achieved. When the amount is more than 50 parts by mass, the curable resin combination is obtained. The storage stability of the material is reduced.

<Formation of cured film>

The curable resin composition is applied to a substrate and cured to form a cured film. The curable resin composition exhibits adhesion to a substrate from the thioether group of the (A) thioether-containing (meth) acrylate derivative. Therefore, the substrate is excellent in adhesion improving effect to a substrate having a chemical bond (high chemical affinity) with a thioether group, for example, a transition metal or an alloy thereof, or a ruthenium compound, a phosphorus compound, a sulfur compound, or a boron compound. An inorganic substrate; 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 substrate such as a plasma or a UV ozone-treated organic substance. Specifically, examples of the inorganic substrate include glass, enamel, various metals, and the like. As the organic substrate, a poly(meth)acrylic resin, a cellulose triacetate (TAC) resin, polyethylene terephthalate (PET) or polybutylene terephthalate is preferably used. Polyester resin, polycarbonate resin, polyimide resin, polyolefin resin such as polyethylene or polypropylene, polycarbonate, polyimine, ABS resin, polyvinyl alcohol, vinyl chloride resin , polyacetal, and the like. Further, in the curable resin composition, since the (A) thioether-containing (meth) acrylate derivative has a specific hydrocarbon group, the cured film is excellent in flexibility. Therefore, even in cold conditions, the cured film easily follows the substrate and is excellent in adhesion to the substrate. It can thus be used particularly suitably for the coating of flexible substrates for use in cold conditions.

The curable resin composition can be cured by irradiation of light. Examples of the irradiation light include active energy rays such as UV (ultraviolet rays) and EB (electron beam). Light irradiation amount of about ^{2 2500mJ} / cm Further, the curable resin composition contained in the case of component (C) may be normally required reduced to about 100mJ / cm ^2. Further, when the curable resin composition contains the component (D), it can be cured at a low temperature of about 80 °C. Further, when the curable resin composition contains the components (C) and (D), it can be cured by a double process of a curing process of light irradiation and a curing process by heating.

In order to make the reaction system uniform and easy to apply, the curable resin composition can be used after being diluted with an organic solvent. Examples of such an organic solvent include an alcohol solvent, an aromatic hydrocarbon solvent, an ether solvent, an ester solvent, and an ether ester solvent, a ketone solvent, and a phosphate solvent. The amount of these organic solvents added is preferably controlled to be less than 10,000 parts by mass with respect to 100 parts by mass of the curable resin composition, but substantially the solvent volatilizes when the cured film is formed, and thus does not greatly affect the physical properties of the cured film.

In addition, a viscosity modifier such as cerium oxide powder may be added to the curable resin composition of the present invention for the purpose of adjusting the viscosity. It is preferable to control the addition amount of these viscosity modifiers to less than 300 mass parts with respect to 100 mass parts of curable resin composition. If the amount of the viscosity modifier added exceeds 300 parts by mass, the adhesion may be lowered.

Further, the curable resin composition of the present invention may also contain various additives which can be used for ordinary coatings or binders. Examples of such an additive include a surfactant for smoothing the coated surface, an aluminum salt for extending the usable time, and the like. It is preferable to control the addition amount of these additives to less than 80 mass parts with respect to 100 mass parts of curable resin composition. If the amount of these additives added exceeds 80 parts by mass, the adhesion may be lowered. Example

The curable resin composition will be more specifically described below by way of examples and comparative examples. The respective components used in the examples and comparative examples are as follows. Further, Mw represents a weight average molecular weight.

<(A) component>

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

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

(A-3: (meth) acrylate derivative containing a sulfide)

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

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

(A-6: polythiol compound)

(A-7: polythiol compound)

(A-8: alkoxydecane derivative containing a sulfide)

(A-9: alkoxydecane derivative containing a sulfide)

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

<(B) component): polyfunctional (meth) acrylate>

(B-1, Mw: 5000) (n average is 13)

(B-2, Mw: 246)

(B-3, Mw: 352)

(B-4, Mw: 22000) A polymer of methacrylic acid was added in an equimolar amount to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using the following D-3 as a catalyst (with hexane pair) 50 wt% of methyl isobutyl ketone solution for reprecipitation to obtain a white solid)

(B-5, Mw: 45000) An equimolar addition of a methacrylic acid polymer to a copolymer of glycidyl methacrylate and cyclohexyl methacrylate using the following D-3 as a catalyst (with hexane pair) 50 wt% of methyl isobutyl ketone solution for reprecipitation to obtain a white solid)

<(C) component: photopolymerization initiator>

(C-1, Mw: 204) 1-hydroxy-cyclohexyl-phenyl-one

(C-2, Mw: 348) 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide

(C-3, Mw: 407) 2-(9-oxanthene-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]non-5-ene

<(D) component: amine compound>

(D-1, Mw: 110)

(D-2, Mw: 102) N , N -dimethyl-1,3-propanediamine

(D-3, Mw: 680) (n1, n2, and n3 are integers of 1 to 5, and an average of 3.5 mixtures)

Each of the components (A) to (D) was mixed with a mixing ratio as shown in the following Tables 1 to 4, and stirred with a spatula to obtain a sample of the curable resin composition of each of the examples and the comparative examples. Each of the curable resin composition samples of the obtained examples and the comparative examples was evaluated for the following adhesion 1 (room temperature adhesion), adhesion 2 (cold area adhesion), flexibility, and storage stability. The results are shown in Tables 1 to 4.

[Production of test piece for evaluation]

The test piece for evaluation of adhesion 1, adhesion 2, and flexibility was obtained as follows. Each sample of the curable resin composition was applied to a 25 mm wide PET film with a thickness of 100 μm by a die coater, and after superimposing another PET film thereon, the curing conditions shown in Tables 1 to 4 were used. The test piece was evaluated by curing. In addition, Lumirror U46-100 manufactured by Toray Industries, Inc. was used as the PET film. The light lamp "light hammer 6" manufactured by Heraeus NobleLight Fusion UV Co., Ltd. was used for the light irradiation, and the bulb was used for the H bulb.

[Adhesiveness 1 (room temperature attachment)]

The test piece for evaluation was allowed to stand at 25 ° C for 24 hours, and then measured by a T-peel method prescribed in JIS K6854-3 within 5 minutes, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PDT film cracking)

○: Tensile strength is 5 N/25 mm or more (PDT film is not broken)

×: less than 5N/25mm

[Attach 2 (cold area attachment)]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then measured by a T-peel method prescribed in JIS K6854-3 within 5 minutes, and evaluated as follows.

◎: Tensile strength is 5N/25mm or more (PDT film cracking)

○: Tensile strength is 5 N/25 mm or more (PDT film is not broken)

×: less than 5N/25mm

[softness]

The test piece for evaluation was allowed to stand at -10 ° C for 24 hours, and then wound on a rod having a diameter of 8 mm for 1 minute within 5 minutes, and visually observed and evaluated as follows.

○: 0 cracks

×: 1 or more cracks

[save stability]

The viscosity of the sample of the curable resin composition of each of the examples and the comparative examples immediately after mixing (the viscosity immediately after mixing) was measured, and the viscosity after heating at 40 ° C for 12 hours (viscosity after heating) was measured again. The viscosity after heating was divided by the viscosity immediately after mixing, and the viscosity increase ratio was calculated, and the following evaluation was performed. In addition, the viscosity was measured by the R-type viscometer manufactured by Toki Sangyo Co., Ltd. under the following conditions.

Rotor used: 1°34’×R24

Measuring range: 0.5183~103.7Pa•s

◎: viscosity increase rate 1.0~1.8

○: viscosity increase rate 1.8~10

×: The viscosity increase rate is outside the above range

[Table 1]

[Table 2]

[table 3]

[Table 4]

In the curable resin compositions of Examples 1-1 to 1-13, high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability were confirmed. In the curable compositions of Examples 2-1 to 2-5, it was confirmed that the film was cured by a small amount of light irradiation, high adhesion at room temperature and cold conditions, good flexibility, and excellent storage stability. In the curable resin compositions of Examples 3-1 to 3-5, it was confirmed that the film was cured by a small amount of light and low-temperature heating, and high adhesion at room temperature and cold conditions, good flexibility, and excellent preservation. stability. On the other hand, in Comparative Example 1-1 in which the component (A) was too small relative to the component (B) and the comparative example 1-2 in which the component (A) was excessively added to the component (B), it was attached not only in cold conditions. Poor sex, poor adhesion at room temperature. In Comparative Examples 1-3 to 1-7 using the compound having the structure of the above formula 1 as the component (A), the adhesion under cold conditions was poor.

no.

no.

no.

Claims (3)

A curable resin composition comprising: (A) a thioether-containing (meth) acrylate derivative represented by the following formula 1: (B) a polyfunctional (meth) having a weight average molecular weight of 200 to 50,000. Acrylate; the mass ratio (A)/(B) of the component (A) to the component (B) is 0.05 to 30, In the formula, a is an integer of 1 to 2, b is an integer of 1 to 2, a + b = 3; R ¹ is a trivalent group represented by the following formula 2, and R ² is a following formula 3 Or a divalent group represented by the following formula 4; and R ³ is a hydrocarbon group having 1 to 12 carbon atoms; R ⁴ in the formula is -CH ₂ -, -CH ₂ CH ₂ -, or -CH ₂ CH(CH ₃ )-, R ⁵ is a hydrogen atom or a methyl group. R ⁵ is a hydrogen atom or a methyl group. The curable resin composition according to claim 1, further comprising 0.01 to 10 parts by mass of (C) photopolymerization per 100 parts by mass of the total mass of the component (A) and the component (B). Starting agent. The curable resin composition according to claim 1 or 2, further comprising 0.01 to 50 parts by mass of (D) based on 100 parts by mass of the total mass of the component (A) and the component (B). The weight average molecular weight is an amine compound of 90 to 700.