KR20210134262A - Photo sensitive type resin composition and solder resist - Google Patents

Abstract

The present invention relates to a photosensitive resin composition capable of minimizing cracking even in a wide temperature range while having heat resistance, adhesion, and adhesion after high temperature storage, and a solder resist comprising a cured product thereof. The present invention is the photosensitive resin composition comprising an acid-modified oligomer, a photoinitiator, talc, and a resin having a core-shell structure, wherein the core of the resin having a core-shell structure is polybutadiene rubber.

Description

Photosensitive resin composition and soldering resist {PHOTO SENSITIVE TYPE RESIN COMPOSITION AND SOLDER RESIST}

The present invention relates to a solder resist comprising a photosensitive resin composition and a cured product thereof.

In the case of parts constituting automobiles, the use of electronic devices was limited in the past, but in recent years the number of parts controlled by a computer has increased, and printed circuit boards (PCBs) are essential for those parts.

Since the durability of the PCB is determined by the reliability of the solder resist, the reliability of the solder resist is essential to secure the durability of the PCB.

In addition, unlike general electronic products, automobiles have a wide operating temperature range and long service life, so it is necessary to secure durability at high temperatures for PCBs used in automobiles.

However, in general, at high temperatures, solder resists have problems such as cracks or reduced adhesion, so a solder resist suitable for a PCB that has a wide operating temperature range and can secure durability for a long time is required.

Accordingly, in the resin composition for forming the solder resist, there has been an attempt to supplement the crack resistance through the synthesis of a new resin. For example, Japanese Patent Publication No. 4328593 (Patent Document 1) uses a curable composition comprising a photosensitive resin to which a carboxyl group and cyclic ether are added and a photosensitive (meth)acrylate compound, and Japanese Patent Publication No. 5298956 (Patent Document 2) attempts to supplement crack resistance by using a photosensitive resin composition containing a bismaleimide compound.

However, the photosensitive resin composition presented in Patent Documents 1 and 2 requires verification of environmental substance registration and regulation, it is difficult to use universally for mass mass production, and there is a problem of inefficiency in terms of economy due to high price.

Japanese Patent No. 4328593 Publication Japanese Patent No. 5298956 Publication

The present invention is a photosensitive resin composition that is easy to use universally for mass mass production, is economically efficient, and has excellent heat resistance, adhesion, and adhesion after high temperature, while minimizing the occurrence of cracks for a long period of time even in a wide temperature range. It aims at providing the soldering resist containing this hardened|cured material.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved with the following photosensitive resin composition.

(1) A photosensitive resin composition comprising an acid-modified oligomer, a photoinitiator, talc, and a resin having a core-shell structure, wherein the core of the resin having a core-shell structure is polybutadiene rubber.

(2) The photosensitive resin composition which further contains alumina in the photosensitive resin composition of said (1).

(3) The alumina is a spherical (spherical) alumina particles having an average particle diameter of 1 to 32 ㎛, the photosensitive resin composition.

(4) The alumina is 15 to 25% by weight of the total content of the composition, the photosensitive resin composition.

(5) The talc has an average particle diameter of 1 to 32 μm, the photosensitive resin composition.

(6) The talc is contained in 2.5 to 10% by weight of the total content of the composition, the photosensitive resin composition.

(7) The core-shell structure of the resin has an average particle diameter of 100 to 500 nm, the photosensitive resin composition.

(8) The core-shell structure of the resin in the total content of the composition, including 5 to 10% by weight, the photosensitive resin composition.

(9) The acid-modified oligomer is a cresol novolac epoxy (meth) acrylate-based compound, the photosensitive resin composition.

(10) The photosensitive resin composition, wherein the shell of the core-shell structure resin is a polymer having affinity with the epoxy resin.

(11) The soldering resist containing the hardened|cured material of the said photosensitive resin composition.

A solder resist comprising the photosensitive resin composition of the present invention and a cured product thereof has excellent crack resistance in a wide temperature range, and excellent heat resistance, adhesion, and adhesion after high temperature storage.

1 is a cross-sectional view showing an example of a core-shell structure resin included in the composition of the present invention.

Generally, it is difficult to secure reliability at high temperature due to the occurrence of cracks at high temperature or the problem of lowering of adhesion. did.

Accordingly, the present inventors have found that it is easy to use universally for mass mass production, is economically efficient, and has excellent heat resistance, adhesion, and adhesion after high temperature storage, while at the same time minimizing the occurrence of cracks in a wide temperature range for a long period of time. Photosensitivity A solder resist comprising a resin composition and a cured product thereof was invented.

The photosensitive resin composition according to the present invention may include an acid-modified oligomer, a photoinitiator, talc, and a resin having a core-shell structure, and the core of the resin having a core-shell structure may be polybutadiene rubber.

In particular, since the photosensitive resin composition contains a combination of a specific inorganic filler, talc, and a specific core-shell structure resin, it can withstand stress due to contraction and expansion of the solder resist when left for a long time at high temperatures as well as at low temperatures. occurrence can be prevented. In addition, the present invention can be used to exhibit good adhesion while maintaining the original properties of a solder resist.

In the present invention, the temperature range of low and high temperature is -40 ℃ to 150 ℃.

(Acid-modified oligomer)

Acid-modified oligomer is an oligomer containing a thermosetting functional carboxyl group and a photocurable functional acrylate group, and a polymerizable monomer having a carboxyl group and/or an acrylate group and an unsaturated double bond and/or an acrylate group. It can be obtained in the form of an oligomer by copolymerizing the monomers containing it. For example, a carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with a compound having an unsaturated double bond such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene; A compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, and a (meth)acryloyl group, and a reactive group such as an epoxy group and acid chloride in a part of the copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond, for example, glycy Carboxylic group containing photosensitive resin obtained by making dil (meth)acrylate react and adding an ethylenically unsaturated group as a pendant; By reacting an unsaturated carboxylic acid with a copolymer of a compound having an epoxy group and an unsaturated double bond, such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and a compound having an unsaturated double bond, a carboxyl group-containing photosensitive resin obtained by reacting a secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride; In a copolymer of an acid anhydride having an unsaturated double bond, such as maleic anhydride and itaconic anhydride, and a compound having an unsaturated double bond, one hydroxyl group, such as hydroxyalkyl (meth)acrylate, and one or more ethylenically unsaturated double bonds Carboxylic group containing photosensitive resin obtained by making the compound which has; a carboxyl group-containing photosensitive resin obtained by introducing an unsaturated double bond into a reaction product of a bisepoxy compound and bisphenol and then reacting a saturated or unsaturated polybasic acid anhydride; Novolak-type phenol resin and alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran and tetrahydropyran and/or ethylene carbonate, propylene carbonate, butylene Carboxylic group-containing obtained by reacting an unsaturated monocarboxylic acid with a reaction product with a cyclic carbonate such as carbonate or 2,3-carbonate propyl methacrylate, and reacting a saturated or unsaturated polybasic acid anhydride with the obtained reaction product It may be a photosensitive resin.

More specific examples of the acid-modified oligomer may include an epoxy (meth)acrylate-based compound. As the epoxy (meth)acrylate-based compound, novolac epoxy, bisphenol A epoxy, bisphenol F epoxy, or the like may be used, and the novolac epoxy may be a cresol novolac epoxy (meth)acrylate-based compound.

Using a novolak epoxy, preferably a cresol novolac epoxy (meth)acrylate-based compound as the acid-modified oligomer, is advantageous in that it can ensure the crosslinking of the coating film and exhibit improved insulation resistance and heat resistance reliability, and is suitable for mass mass production. Therefore, it is easy to use universally and is economically efficient.

(Photoinitiator)

The photopolymerization initiator of the present invention may be used without any particular limitation, and may be used alone or as a mixture of two or more types.

Examples of the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4′) Aminoacetophenones such as -morpholinophenyl)-1-butanone and N,N-dimethyl aminoacetophenone; bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-di A titanocene compound such as fluoro-3-(1H-pyrrol-1-yl)phenyl)titanium can be used.

Further, for example, benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone Acetophenones such as , 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetphenone; 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinones such as anthraquinone; thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Organic peroxides such as benzoylphaoxyside and cumenephaoxyside; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutylate; 2-mercapto thiol compounds such as benzimidazole, 2-mercaptobenzooxazole, and 2-mercaptobentocyazole; 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, and tribromide; organic halogen compounds such as momethylphenylsulfone; benzophenones or xanthones such as benzophenone and 4,4-bisdiethyl aminobenzophenone; 2,4,6-trimethylbenzoyldiphenyl phosphine oxide and the like, It is not limited to these.

Preferably, the photopolymerization initiator is aminoacetophenone; or titanocenes, more preferably 2-benzyl-2-dimethylamino-1-(4'-morpholinophenyl)-1-butanone; or bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, using such a photopolymerization initiator The coating film formed by doing this has the advantage of being able to form a high-resolution pattern.

(Inorganic filler)

The present invention may include talc and, if necessary, may further include a material that can be used as an inorganic filler.

The average particle diameter of the talc of the present invention may be 1 to 32 μm. When the average particle diameter of the talc satisfies the above range, it is advantageous in that the printability is good because it is not exposed on the surface of the resist having a size of about 15 to 30 μm. If the average particle diameter of the talc is less than 1 ㎛, the oil absorption is high, the fluidity is poor and the printability is poor.

The content of the talc may include 2.5 to 10% by weight, preferably 2.5 to 6% by weight based on the total content of the composition. When the content of talc included in the composition is within the above range, it is possible to reduce a mismatch in coefficient of thermal expansion (CTE) between the solder resist and the substrate, thereby exhibiting excellent crack resistance.

Alumina may be further included as a material that can be used as the inorganic filler. In this case, a mismatch in coefficient of thermal expansion (CTE) between the solder resist and the substrate may be reduced, thereby exhibiting more excellent crack resistance.

The alumina may be spherical alumina particles having an average particle diameter of 1 to 32 μm. When the average particle diameter of alumina satisfies the above range, it is advantageous in that the printability is good because it is not exposed on the surface of the resist having a size of about 15 to 30 μm. When the average particle diameter of alumina is less than 1 μm, the oil absorption is high, the fluidity is poor and the printability is poor. . In addition, when spherical alumina particles are used as alumina, it is preferable in terms of easy dispersion during resist production.

The content of the alumina may include 15 to 25% by weight based on the total content of the composition. When the content of alumina included in the composition is within the above range, it is possible to reduce the mismatch in the coefficient of thermal expansion (CTE) between the solder resist and the substrate, thereby exhibiting excellent crack resistance. Moreover, it shows the adhesiveness excellent even after leaving it high temperature.

(resin with core-shell structure)

The present invention may include a resin having a core-shell structure, and in the resin having a core-shell structure, the core may be polybutadiene rubber.

1 is a representative cross-sectional view showing an example of a resin having a core-shell structure of the present invention.

The core-shell structure of the resin is an elastomer with excellent flexibility, and by being included in the photosensitive resin composition, it can withstand the stress caused by the shrinkage and expansion of the solder resist at high temperatures as well as low temperatures, thereby contributing to the excellent crack resistance of the photosensitive resin composition. .

In the resin having the core-shell structure, the shell may be a polymer having affinity for the epoxy resin. As the polymer having affinity with the epoxy resin, for example, an acrylic polymer or the like can be used.

Having affinity with the epoxy resin indicates that the epoxy resin exhibits a high compatibility property, and thus can have a high bonding strength with the epoxy resin.

The resin of the core-shell structure may have an average particle diameter of 100 to 500 nm, and may be included in an amount of 5 to 10% by weight of the total content of the composition.

A commercially available product may be used as the core-shell structure resin. For example, MX-267 manufactured by KANEKA, which is a core-shell structure resin having a core containing 37 wt% of polybutadiene, may be used. .

(etc)

In the present invention, the photosensitive resin composition may further include at least one of a pigment, an additive, and an antioxidant.

Pigments that may be included in the composition may include blue, green, yellow pigments and the like. The blue pigment may be phthalocyanine blue, pigment blue 15:1, pigment blue 15:2, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 60, etc., It is not limited thereto. The green pigment may be Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like, but is not limited thereto. Yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones, for example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, and Pigment. Yellow 181, Pigment Yellow 193, etc. may be, but is not limited thereto.

Additives that may be included in the composition include known and customary thickeners such as finely divided silica, organic bentonite, and montmorillonite; Antifoaming agents or leveling agents, such as a silicone type, a fluorine type, and a polymer type; Silane coupling agents, such as an imidazole type, a thiazole type, and a triazole type; flame retardants such as phosphorus-based flame retardants and antimony-based flame retardants; and the like, but is not limited thereto.

The antioxidant that may be included in the composition may be a phenol-based compound, a phosphorus-based compound, a thiol-based compound, and the like, but is not limited thereto. For example, a phenolic compound is BHT (made by UCP); AO-50 (manufactured by Hannong ADEKA), or AO-60 (manufactured by Hannong ADEKA); Santowhite PC (manufactured by Monsanto) or the like. For example, the phosphorus compound is Mianto P-600 (manufactured by Miwon Corporation) or Mianto P-650 (manufactured by Miwon Corporation); KP 1460 (manufactured by Kolon Petrochemical) and the like. For example, the thiol-based compound may be Mianto-L (manufactured by Miwon Corporation), Mianto-S (manufactured by Miwon Corporation), or the like.

In addition, the photosensitive resin composition of the present invention may further include at least one of a thermosetting resin, a photopolymerizable monomer, a thermosetting agent, and a solvent.

Thermosetting resins that may be included in the composition include cresol novolac epoxy resins, phenol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, N-glycidyl type epoxy resins, bisphenol A novolac epoxy resins, Bixylenol epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, hetero It may be a cyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin, ε-caprolactone-modified epoxy resin, heterocyclic epoxy resin, and the like, but is not limited thereto. Preferably, the thermosetting resin is an epoxy resin, more preferably a phenol novolac epoxy resin or a bisphenol A epoxy resin.

The photopolymerizable monomer that may be included in the composition may be an acrylate-based compound having two or more photocurable unsaturated functional groups, and specific examples thereof include 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaeryth. hydroxyl group-containing acrylate-based compounds such as ritol pentaacrylate; water-soluble acrylate-based compounds such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; acrylate-based compounds of polyfunctional alcohols such as trimethylolpropane or hydrogenated bisphenol A or ethylene oxide adducts and/or propylene oxide adducts of polyhydric phenols such as bisphenol A and biphenol; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, or an epoxy acrylate compound which is a (meth)acrylic acid adduct of a phenol novolac epoxy resin; Caprolactone-modified acrylate compounds such as caprolactone-modified ditrimethylolpropanetetraacrylate, ε-caprolactone-modified dipentaerythritol acrylate, or caprolactone-modified hydroxypivalate neopentyl glycol ester diacrylate However, it is not limited thereto.

Thermal curing agents that may be included in the composition include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine compound; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine; Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct It may be an S-triazine derivative such as, but is not limited thereto.

The solvent that may be included in the composition includes ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl glycol ethers such as ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Acetic acid esters, such as; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, and carbitol; aliphatic hydrocarbons such as octane and decane; It may be a petroleum solvent such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, but is not limited thereto.

(Solder Resist)

The solder resist of the present invention may include a cured product of the photosensitive resin composition.

The cured product of the photosensitive resin composition of the present invention can be obtained by screen printing the resin composition and curing (photocuring), specifically, it is applied by a screen printing method and contained in the composition at a temperature of about 70 to 90 ° C. It can be obtained by a method of forming a coating film by volatilizing and drying an organic solvent, forming a pattern by a contact exposure machine, developing an unexposed area with an aqueous alkali solution, and thermally curing the resist pattern at a temperature of 140 to 160 ° C.

The solder resist, while maintaining the original characteristics of the solder resist in a wide temperature range, prevents the occurrence of cracks and exhibits good adhesion, thereby exhibiting high reliability for a long period of time.

The solder resist may be included in a PCB that requires high durability and is preferably used as a component of an automobile having a long-term use period of about 10 to 30 years. can be maintained and used.

Example

Hereinafter, although the resin composition of this invention is demonstrated by an Example, this invention is not limited to a following example.

The components shown in Table 1 (based on weight %) are divided into 1) to 10) (subject) and 11) to 16) (curing agent) and each pre-mixed in a stirrer, followed by 3-Roll-Mill (3-Roll-Mill, BUHLER, SDY-300). Thereafter, a resin composition was prepared by mixing the main agent and the curing agent.

ingredient

1) Acid-modified cresol novolac epoxy acrylate (DIC)

2) Acid-modified cresol novolac epoxy acrylate (DIC)

3) Blue pigment and yellow pigment (manufactured by Taiyo ink Korea)

4) Containing at least one of a foam destroying polymer (manufactured by BYK-Chemie GmbH), silicone oil (manufactured by Shin-Etsu), and polyhydroxy carboxylic acid ester (manufactured by BYK-Chemie GmbH) additive to

5) Phenolic compounds (manufactured by Adeka Korea)

6) bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium (manufactured by UFC Corporation), and 2-Benzyl-2-dimethylamino-4'-morpholinobutyrophenone (manufactured by UFC Corporation)

7) Barium sulfate (D50: 0.3㎛, manufactured by Foshan Onmillion Nano Materials)

8) Talc (D50: 4.7㎛, manufactured by KOCH)

9) Spherical alumina (D50: 2.0㎛, manufactured by Denka)

10) Spherical alumina (D50: 5.1㎛, manufactured by Denka)

11) Thermosetting resin comprising at least one of phenol novolac epoxy (manufactured by DIC), bisphenol A epoxy (manufactured by DIC), and diallyl phthalate resin (manufactured by OSAKA SODA)

12) Dipentaerythritol hexaacrylate (manufactured by Miwon Specialty Chemicals)

13) Resin of core-shell structure having a core containing 37% by weight of polybutadiene (manufactured by KANEKA)

14) Epoxidized polybutadiene (epoxy equivalent: 193 g/eq) (manufactured by DAICEL)

15) Melamine (manufactured by JingShan Ink Material)

16) Dipropylene glycol monomethyl ether (manufactured by Dow chemical)

Specimen production

The copper foil-laminated substrate on the FR-4 substrate _{was pretreated with H 3} PO ₄ 5wt%, Brush 600#, 800#. After printing the inks prepared in Examples and Comparative Examples using a 120# screen, drying in an oven box at 90° C. for 15 minutes to volatilize the solvent, and then attaching a negative type photomask to the specimen After that, it was exposed at an exposure dose of ^{400 mJ/cm 2} with an OTS scattered light exposure machine. Thereafter, after development in 30° C. Na ₂ CO ₃ 1wt% aqueous solution, a pattern was formed. After curing for 1 hour in an oven box at 160° C., it was exposed at an exposure amount of ^{1000 mJ/cm 2 in a UV bumper such as metal.}

Evaluation item 1: Crack resistance

After 500 cycles of the specimen prepared according to the specimen preparation method using a thermal shock device (ETAC), a temperature of -40 ° C., 15 minutes holding (holding), 150 ° C., 15 minutes holding (holding) as 1 cycle, Specimens were measured under a microscope and evaluated according to the following criteria.

Number of cracks in 58 sections

1: No cracks

2: 1~10 cracks occur

3: 11~20 cracks occurred

4: 21 to 30 cracks occur

5: 31~40 cracks occurred

6: 41 to 50 cracks

7: More than 50 cracks

Evaluation item 2: Adhesion

The specimens prepared according to the specimen preparation method were cross-cut with a cross hatch cutter (manufactured by Yoshimitsu), and after a tape test, the specimens were measured with a microscope and evaluated according to the following criteria.

2:

3.

One:

2:

3.

Evaluation item 3: Heat resistance

After floating the specimen produced according to the above specimen manufacturing method at 265 ° C. for 10 seconds 3 times in a heat-resistant round dazzle (model name: HY-1000), after the tape test, the specimen was visually observed and the following criteria were used. evaluated.

1: No peeling.

2: There is peeling.

Evaluation item 4: Adhesion after leaving at high temperature

After holding the specimen prepared according to the specimen preparation method at 150° C. for 1000 hours in an oven box, the specimen is cross-cut with a cross hatch cutter (Cross Hatch Cutter, manufactured by Yoshimitsu), and then the tape After the test, the specimen was measured under a microscope and evaluated according to the following criteria.

2:

3.

One:

2:

3.

The measured results of the evaluation items 1 to 4 are shown in Table 2.

As can be seen from the results in Table 2, the compositions of Examples 1 to 6 are excellent in adhesion, heat resistance and adhesion after high temperature, and at the same time have excellent physical properties compared to the compositions of Comparative Examples 1 to 6 in crack resistance have

Claims (1)

All inventions described in the Detailed Description of the Invention.

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