KR101260514B1 - Hyperbranch polymer and preparation method thereof, and negative photosensitive resin composition containing the polymer - Google Patents

Abstract

The present invention relates to a hyperbranched polymer, a method for preparing the same, and a negative photosensitive resin composition including the same, wherein a hyperbranched structure is formed by performing a condensation reaction of a mixture of a diol and a multiol compound and a diisocyanate compound during the preparation of the hyperbranched polymer. It forms, and introduce | transduces a desired acid value by making an acid anhydride react, and provides low viscosity and developability in the photosensitive resin composition.

Hyper Branch, Urethane, Photosensitive Resin, Diisocyanate

Description

Hyperbranched polymer and preparation method thereof, and negative photosensitive resin composition comprising the same

The present invention relates to a hyperbranched polymer, a method for preparing the same, and a negative photosensitive resin composition including the same, wherein a hyperbranched structure is obtained by performing a condensation reaction of a mixture of a diol and a multiol compound and a diisocyanate compound when the hyperbranched polymer is prepared. The present invention relates to a photosensitive resin composition which is formed and further reacts with an acid anhydride to introduce a desired acid value, thereby ensuring low viscosity and developability.

The resin used in the initial photosensitive resin composition is an acrylate type, which was mainly synthesized through radical polymerization. In the case of acrylate resin, alkali developability is imparted by superposing | polymerizing together the acryl monomer containing an acidic radical. However, gradually higher sensitivity to the composition has been developed in the direction of improving the sensitivity by introducing an unsaturated double bond in the resin. In this case, the viscosity increase effect in the synthesis process to increase the content of the unsaturated double bonds is rapidly increased, causing a limit to the unsaturated double defect content. In addition, the acrylic resin is difficult to overcome the inherent limitations, such as heat resistance because the majority of the main chain is made of a carbon-carbon single bond. Therefore, in recent years, research on condensation polymerization type resins that may include benzene rings or various functional groups in the main chain is active, and a urethane resin is one of them. Urethane-based resins have a very high content of unsaturated double bonds that can be included, excellent adhesion due to the polarity of the urethane bonds, and exhibits excellent heat resistance characteristics due to high bonding energy of the urethane. On the other hand, due to the hydrogen bonding of the urethane, etc., the viscosity increase is very large according to the molecular weight is a disadvantage. In the present invention, by introducing a hyperbranched structure to improve this disadvantage of the urethane-based resin.

The present invention is to solve the above problems, while maintaining the adhesiveness, heat resistance, sensitivity of the urethane-based resin, and at the same time the synthesis of a urethane-based resin polymer comprising a hyperbranched structure effective for improving the low viscosity, developability and It aims at providing the negative photosensitive resin composition containing this.

The present invention is to achieve the above object, to provide a hyperbranched polymer produced by the reaction of the compounds represented by the formula (1) to formula (4).

[Formula 1]

(Z는 직접 결합 또는 C₁ 내지 C₆의 알킬렌, 케톤, -O-, -S-, -SO₂-, 헥사플루오로프로필렌, -OC₆H₄O-, 및 -OC₆H₄C(CH₃)₂C₆H₄O-로 이루어지는 군으로부터 선택되는 어느 하나이다) 중 선택된 하나이고, R₂는 수소 혹은 메틸 중 선택된 하나이고, R₃은 각각 독립적으로 수소 혹은 C₁-C₄의 알킬기 중 선택된 하나이다.)Wherein R ₁ is 1 to 10 alkylene,-(CH ₂ CH ₂ O) _n CH ₂ CH _2- (n is an integer of 1 to 10),-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH ₂ -(n is an integer from 1 to 10),

(Z is a direct bond or C ₁ to C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropylene, -OC ₆ H ₄ O-, and -OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O-), and R ₂ is selected from hydrogen or methyl, and R ₃ is each independently hydrogen or C ₁ -C ₄ . One of the alkyl groups.)

[Formula 2]

(The above formula, R ₄ is a hydroxy group, C ₁ ~ C ₈ alkyl, C ₁ ~ C ₆ alkyl esters, hydroxyl 1-2 dogs substituted C ₁ -C ₆ alkyl esters, C ₁ ~ C ₃ alkoxy group optionally substituted C ₂ ~ C ₆ alkyl esters, substituted by halogen C ₁ ~ C ₆ alkyl ester of a C ₁ ~ C ₆ substituted by phenyl esters, substituted with an alkyl group of C ₁ ~ C ₆ phenyl, C ₁ ~ Phenyl substituted by C ₆ alkoxy, phenyl substituted by halogen group, R ₅ is C ₁ -C ₈ alkyl, C ₁ -C ₆ alkyl ester, C ₁ -C ₃ alkoxy group C ₂ ~ C ₆ alkyl esters, substituted by halogen C ₁ ~ C ₆ alkyl ester of a C ₁ ~ C ₆ substituted by phenyl esters, substituted with an alkyl group of C ₁ ~ C ₆ phenyl, C ₁ ~ C ₆ alkoxy is one selected from a phenyl, the group composed of a binary phenyl substituted by halogen substituted, R ₆ may be directly connected, the C ₁ ~ C ₈ alkyl , One of the C ₁ to the phenylene group substituted with alkyl groups of C ₆ alkylene ester, the C ₁ to C ₆ alkylene ester, C ₁ to C ₆ substituted by phenyl.)

(3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene or alkylene ester, C ₁ to C ₆ alkylene ester substituted with phenyl group, C ₁ to C ₆ alkyl group, alkoxy group or halogen substituted It is one of the group consisting of cyclohexylene substituted with one or more phenylene, methyl or ethyl substituent, and biphenylene substituted with one or several alkyl groups of C ₁ to C _3. )

[Formula 4]

(In the formula, R _8, R ₉ is cyclohexane or bicyclo hexyne (where, C ₁ -C ₃ is C ₁ -C ₁₀ alkyl, C ₁ -C ₅ alkyl esters, R ₈ and R ₉ each connected to one another May be substituted with alkyl), phenyl, phenyl substituted with carboxylic acid, or one or more alkyl groups of C ₁ -C ₂ substituted biphenyl.)

In addition, the compound represented by Formula 4 is succinic anhydride, glutaric anhydride, methyl succinic anhydride, maleic anhydride, methyl maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4 And 5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride or cis-5-norbornene- (endo, exo) -2,3-dicarboxylic acid anhydride.

In addition, the weight average molecular weight of the hyperbranched polymer is characterized in that 1000 to 50000g / mol.

In addition, the present invention comprises the steps of reacting the compound represented by the formula (1) and the compound represented by the formula (2) in the solvent and the compound represented by the formula (3) to generate a urethane bond; And it provides a method for producing a hyperbranched polymer comprising the step of reacting by adding a compound represented by the following formula (4) to the reactant.

[Formula 1]

(Z는 직접 결합 또는 C₁ 내지 C₆의 알킬렌, 케톤, -O-, -S-, -SO₂-, 헥사플루오로프로필렌, -OC₆H₄O-, 및 -OC₆H₄C(CH₃)₂C₆H₄O-로 이루어지는 군으로부터 선택되는 어느 하나이다) 중 선택된 하나이고, R₂는 수소 혹은 메틸 중 선택된 하나이고, R₃은 각각 독립적으로 수소 혹은 C₁-C₄의 알킬기 중 선택된 하나이다.)Wherein R ₁ is 1 to 10 alkylene,-(CH ₂ CH ₂ O) _n CH ₂ CH _2- (n is an integer of 1 to 10),-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH ₂ -(n is an integer from 1 to 10),

(Z is a direct bond or C ₁ to C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropylene, -OC ₆ H ₄ O-, and -OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O-), and R ₂ is selected from hydrogen or methyl, and R ₃ is each independently hydrogen or C ₁ -C ₄ . One of the alkyl groups.)

[Formula 2]

(The above formula, R ₄ is a hydroxy group, C ₁ ~ C ₈ alkyl, C ₁ ~ C ₆ alkyl esters, hydroxyl 1-2 dogs substituted C ₁ -C ₆ alkyl esters, C ₁ ~ C ₃ alkoxy group optionally substituted C ₂ ~ C ₆ alkyl esters, substituted by halogen C ₁ ~ C ₆ alkyl ester of a C ₁ ~ C ₆ substituted by phenyl esters, substituted with an alkyl group of C ₁ ~ C ₆ phenyl, C ₁ ~ Phenyl substituted by C ₆ alkoxy, phenyl substituted by halogen group, R ₅ is C ₁ -C ₈ alkyl, C ₁ -C ₆ alkyl ester, C ₁ -C ₃ alkoxy group C ₂ ~ C ₆ alkyl esters, substituted by halogen C ₁ ~ C ₆ alkyl ester of a C ₁ ~ C ₆ substituted by phenyl esters, substituted with an alkyl group of C ₁ ~ C ₆ phenyl, C ₁ ~ Phenyl substituted by C ₆ alkoxy, phenyl substituted by halogen group, R ₆ is directly connected, or C ₁ ~ C ₈ alkylene , C ₁ to C ₆ alkylene ester, C ₁ to C ₆ alkylene ester substituted with phenyl group, C ₁ to C ₆ alkyl group substituted with phenylene.)

(3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene or alkylene ester, C ₁ to C ₆ alkylene ester substituted with phenyl group, C ₁ to C ₆ alkyl group, alkoxy group or halogen substituted It is one of the group consisting of cyclohexylene substituted with one or more phenylene, methyl or ethyl substituent, and biphenylene substituted with one or several alkyl groups of C ₁ to C _3. )

[Formula 4]

(In the formula, R _8, R ₉ is cyclohexane or bicyclo hexyne (where, C ₁ -C ₃ is C ₁ -C ₁₀ alkyl, C ₁ -C ₅ alkyl esters, R ₈ and R ₉ each connected to one another May be substituted with alkyl), phenyl, phenyl substituted with carboxylic acid, or one or more alkyl groups of C ₁ -C ₂ substituted biphenyl.)

 In addition, the content ratio of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is 1.0: 0.05 to 1.0: 0.7.

In addition, the equivalent ratio of the compound represented by the formula (1) and the compound represented by the formula (2) and the compound represented by the formula (3) is characterized in that 1.0: 0.5 ~ 1.0: 0.99.

In addition, the compound represented by Formula 4 is trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Butylenediisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'-diisocyanate-1,3-dimethylbenzene, w, w'-diisocyanate-1,4-dimethyl Benzene, w, w'-diisocyanate-1,3-diethylbenzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, isophorone diisocyanate, 1,3-cyclopentanedi Isocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'- Ethylene bis isocyanatomethyl cyclohexane, 2,5-diisocyanate-methyl-bicyclo [2,2,2] heptane is characterized in that the, or 2, 6-isocyanatemethyl-bicyclo [2,2,1] heptane.

The present invention also provides a photosensitive resin composition comprising the hyperbranched polymer, a solvent, a multifunctional crosslinking agent, a photoinitiator, and a color pigment.

In addition, the content of the hyperbranched polymer is characterized in that 1 to 20% by weight based on the total photosensitive resin composition.

In addition, the solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, ethyl acetate , Butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, methyl phthalate, ethyl benzoate, methoxypropyl acetate, toluene, xylene, benzene, ethylbenzene, carbon tetrachloride, trichloroethylene, chloroform, 1,1,1- Trichloroethane, methylene chloride, monochlorobenzene, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide Side, or sulfolane.

In addition, the multifunctional crosslinking agent is polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) Acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, neopentylglycol (meth) acrylate, pentaerythritol tetra acrylate, pentaerythritol triacrylate, dipentaerythritol penta acrylate, or di Pentaerythritol hexa acrylate.

In addition, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine , 2,4-trichloromethyl- (pipelonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Tetraphenyl biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one (Irgacure- 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O-acyl oxime compound, 4,4'-bis (di Methylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide , 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin , 3-benzoyl-7-methoxy-coumarin, or 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- Cl] -benzopyrano [6,7,8-ij] -quinolizine-11-one.

The photosensitive resin composition may further include a surfactant, a filler, an antifoaming agent, a flame retardant, an antioxidant, or a mixture thereof.

When the hyperbranched polymer of the present invention is applied to the photosensitive resin composition, by using a diol compound having an unsaturated double bond, the proportion of the reactive group of the unsaturated double bond in the total resin is high, so that the sensitivity is maintained at the same or higher, and the original urethane resin It can have the adhesiveness and heat resistance of the characteristics, and by having a hyperbranched structure can obtain a viscosity improving effect, which is one of the weak points of the urethane binder, it is possible to obtain the effect of increasing the developability.

The present invention relates to a hyperbranched polymer produced by the reaction of compounds represented by the following formulas (1) to (4).

[Formula 1]

(Z는 직접 결합 또는 C₁ 내지 C₆의 알킬렌, 케톤, -O-, -S-, -SO₂-, 헥사플루오로프로필렌, -OC₆H₄O-, 및 -OC₆H₄C(CH₃)₂C₆H₄O-로 이루어지는 군으로부터 선택되는 어느 하나이다) 중 선택된 하나이고, R₂는 수소 혹은 메틸 중 선택된 하나이고, R₃은 각각 독립적으로 수소 혹은 C₁-C₄의 알킬기 중 선택된 하나이다.)Wherein R ₁ is 1 to 10 alkylene,-(CH ₂ CH ₂ O) _n CH ₂ CH _2- (n is an integer of 1 to 10),-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH ₂ -(n is an integer from 1 to 10),

(Z is a direct bond or C ₁ to C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropylene, -OC ₆ H ₄ O-, and -OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O-), and R ₂ is selected from hydrogen or methyl, and R ₃ is each independently hydrogen or C ₁ -C ₄ . One of the alkyl groups.)

[Formula 2]

(Wherein, R ₄ is a hydroxy group, C ₁ ~ C ₈ alkyl, C ₁ ~ C ₆ alkyl esters, hydroxyalkyl of 1 to 2 when the lock pieces substituted C ₁ -C ₆ alkyl esters, C ₁ ~ C ₃ alkoxy groups A substituted C ₂ to C ₆ alkyl ester, a halogen substituted C ₁ to C ₆ alkyl ester, a phenyl group substituted C ₁ to C ₆ alkyl ester, a C ₁ to C ₆ alkyl group substituted, C Phenyl substituted by ₁ to C ₆ alkoxy, phenyl substituted by halogen group, and R ₅ is C ₁ to C ₈ alkyl, C ₁ to C ₆ alkyl ester, C ₁ to C ₃ alkoxy group A substituted C ₂ to C ₆ alkyl ester, a halogen substituted C ₁ to C ₆ alkyl ester, a phenyl group substituted C ₁ to C ₆ alkyl ester, a C ₁ to C ₆ alkyl group substituted, C ₁ ~ C ₆ alkoxy is one selected from a phenyl, the group consisting of phenyl substituted by halogen substituted, R ₆ may be directly connected, alkyl of C ₁ ~ C ₈ , One of the C ₁ to the phenylene group substituted with alkyl groups of C ₆ alkylene ester, the C ₁ to C ₆ alkylene ester, C ₁ to C ₆ substituted by phenyl.)

(3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene or alkylene ester, C ₁ to C ₆ alkylene ester substituted with phenyl group, C ₁ to C ₆ alkyl group, alkoxy group or halogen substituted It is one of the group consisting of cyclohexylene substituted with one or more phenylene, methyl or ethyl substituent, and biphenylene substituted with one or more alkyl groups of C ₁ to C _3. )

[Formula 4]

(In the formula, R _8, R ₉ is cyclohexane or bicyclo hexyne (where, C ₁ -C ₃ is C ₁ -C ₁₀ alkyl, C ₁ -C ₅ alkyl esters, R ₈ and R ₉ each connected to one another May be substituted with alkyl), phenyl, phenyl substituted with carboxylic acid, or one or more alkyl groups of C ₁ -C ₂ substituted biphenyl.)

Hereinafter, the present invention will be described in detail.

Formula 1 is a diol unit that reacts with a diisocyanate functional group to produce a urethane polymer, and the compound of Formula 2 is a multiol unit that forms a branched structure that is the core of the binder. In addition, the compound represented by the formula (3) is a substance having a diisocyanate functional group to produce a urethane polymer, and is a part that reacts with the extra hydroxyl group represented by the formula (4) to give an acid group to the polymer.

As the compound represented by Formula 4, the acid anhydride used in the present invention is succinic anhydride, methyl succinic anhydride, maleic anhydride, methyl maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3 And 4,5,6-tetrahydrophthalic anhydride and hexahydrophthalic anhydride, but are not limited thereto.

The hyperbranched polymer according to the invention preferably has a weight average molecular weight of 1,000 to 50,000. If the weight average molecular weight is less than 1,000, it is not preferable because the properties such as heat resistance, adhesiveness, residual film ratio, etc. are deteriorated. If the weight average molecular weight is more than 50,000, the synthesis is difficult due to problems such as viscosity increase or gelation in the synthesis process.

The present invention also provides a method for producing a hyperbranched polymer as described below.

(a) reacting a compound represented by Formula 1 with a compound represented by Formula 2 with a compound represented by Formula 3 in a solvent to generate a urethane bond; And

(b) adding and reacting the compound represented by the following formula (4) to the reactant.

[Formula 1]

(Z는 직접 결합 또는 C₁ 내지 C₆의 알킬렌, 케톤, -O-, -S-, -SO₂-, 헥사플루오로프로필렌, -OC₆H₄O-, 및 -OC₆H₄C(CH₃)₂C₆H₄O-로 이루어지는 군으로부터 선택되는 어느 하나이다) 중 선택된 하나이고, R₂는 수소 혹은 메틸 중 선택된 하나이고, R₃은 각각 독립적으로 수소 혹은 C₁-C₄의 알킬기 중 선택된 하나이다.)Wherein R ₁ is 1 to 10 alkylene,-(CH ₂ CH ₂ O) _n CH ₂ CH _2- (n is an integer of 1 to 10),-(CHCH ₃ CH ₂ ) _n OCHCH ₃ CH ₂ -(n is an integer from 1 to 10),

(Z is a direct bond or C ₁ to C ₆ alkylene, ketone, -O-, -S-, -SO _2- , hexafluoropropylene, -OC ₆ H ₄ O-, and -OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₄ O-), and R ₂ is selected from hydrogen or methyl, and R ₃ is each independently hydrogen or C ₁ -C ₄ . One of the alkyl groups.)

[Formula 2]

(Wherein, R ₄ is a hydroxy group, C ₁ ~ C ₈ alkyl, C ₁ ~ C ₆ alkyl esters, hydroxyalkyl of 1 to 2 when the lock pieces substituted C ₁ -C ₆ alkyl esters, C ₁ ~ C ₃ alkoxy groups A substituted C ₂ to C ₆ alkyl ester, a halogen substituted C ₁ to C ₆ alkyl ester, a phenyl group substituted C ₁ to C ₆ alkyl ester, a C ₁ to C ₆ alkyl group substituted, C Phenyl substituted by ₁ to C ₆ alkoxy, phenyl substituted by halogen group, and R ₅ is C ₁ to C ₈ alkyl, C ₁ to C ₆ alkyl ester, C ₁ to C ₃ alkoxy group A substituted C ₂ to C ₆ alkyl ester, a halogen substituted C ₁ to C ₆ alkyl ester, a phenyl group substituted C ₁ to C ₆ alkyl ester, a C ₁ to C ₆ alkyl group substituted, C ₁ ~ C ₆ alkoxy is one selected from a phenyl, the group consisting of phenyl substituted by halogen substituted, R ₆ may be directly connected, alkyl of C ₁ ~ C ₈ , One of the C ₁ to the phenylene group substituted with alkyl groups of C ₆ alkylene ester, the C ₁ to C ₆ alkylene ester, C ₁ to C ₆ substituted by phenyl.)

(3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene or alkylene ester, C ₁ to C ₆ alkylene ester substituted with phenyl group, C ₁ to C ₆ alkyl group, alkoxy group or halogen substituted It is one of the group consisting of cyclohexylene substituted with one or more phenylene, methyl or ethyl substituent, and biphenylene substituted with one or more alkyl groups of C ₁ to C _3. )

[Formula 4]

(In the formula, R _8, R ₉ is cyclohexane or bicyclo hexyne (where, C ₁ -C ₃ is C ₁ -C ₁₀ alkyl, C ₁ -C ₅ alkyl esters, R ₈ and R ₉ each connected to one another May be substituted with alkyl), phenyl, phenyl substituted with carboxylic acid, or one or more alkyl groups of C ₁ -C ₂ substituted biphenyl.)

Hereinafter, the manufacturing method is explained concretely.

(a) The first step is to react a compound of Formula 1 and a compound of Formula 2 with a compound of Formula 3, wherein an excess of alcohol (a mixture of diols and multiols) having an unsaturated double bond is mixed with diisocyanate and aprotic It is a step of adding a known catalyst of activity in a solvent and heating to generate a urethane bond.

In the first step, the ratio between the compound of Formula 1 and the compound of Formula 2 is 1.0: 0.05 to 1.0: 0.7, between the mixture of the compound of Formula 1 and the compound of Formula 2 and the diisocyanate as a compound of Formula 3 The reaction equivalence ratio of is 1.0: 0.5 to 1.0: 0.99, and an excess alcohol compound is used. In this case, the proportion of the unsaturated double bond, which is a reactive group of the diol compound, in the total resin becomes high, so that a sensitivity improvement effect can be obtained, and all reactions can be performed without leaving unreacted isocyanate groups that impair storage stability.

It is also possible to introduce branch structures into the polymer by reacting the multiol compound with the diol compound, which leads to the effect of reducing the viscosity and increasing the developability of the composition comprising the synthesized polymer.

In the present invention, specific examples of the diisocyanate which is the compound of the formula (3) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenedi Isocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'-diisocyanate-1,3-dimethylbenzene, w, w'-diisocyanate -1,4-dimethylbenzene, w, w'-diisocyanate-1,3-diethylbenzene, 1,4-tetramethyl xylene diisocyanate, 1,3-tetramethyl xylene diisocyanate, isophorone diisocyanate, 1 , 3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-shi Clohexane diisocyanate, 4,4'-methylene bis isocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo [2,2,2] heptane, and 2,6-isocyanatemethyl bicyclo [2,2,1] But is not limited to one selected from the group consisting of heptanes.

(b) The second step reaction of the present invention is a step of introducing an acid value by further adding an acid anhydride which is a compound of Formula 4 to react with the alcohol remaining in the excess diol compound used in the first step reaction.

That is, in the present invention, unlike the conventional ester polymers that make ester bonds by using diol compounds and dianhydride compounds and react the epoxy compounds with the resulting high acid groups to introduce unsaturated double bonds and control the acid groups, the acid anhydride in the first step Without the addition, the urethane bond is formed and added during the two-step reaction to react with the remaining alcohol, so that the acid value is introduced, there is an advantage that the acid value can be easily adjusted to a low state. In addition, the finally obtained polymer contains a urethane bond, thereby ensuring development margin, chemical resistance and adhesion.

On the other hand, this invention also has the characteristics in providing the photosensitive resin composition containing the said hyperbranched polymer.

The photosensitive resin composition according to the present invention comprises 1) the hyperbranched polymer as a binder resin, and includes 2) a solvent, 3) a polyfunctional crosslinking agent, 4) a photoinitiator, 5) a colored pigment, and the like, as necessary. It may further include other ingredients.

The 1) hyperbranched polymer of the binder resin of the present invention is preferably contained in 1 to 20% by weight of the total photosensitive resin composition in terms of processability.

In addition to the hyperbranched polymer, the photosensitive resin composition of the present invention may further contain other resins such as urethane resins, polyester resins, and acrylic resins.

The solvent 2) of the present invention is not particularly limited and may be appropriately selected according to the purpose. Specific examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexa At least one alcohol selected from the group consisting of knols;

Ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone;

Esters selected from the group consisting of ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, methyl phthalate, ethyl benzoate, and methoxypropyl acetate;

Aromatic hydrocarbons selected from the group consisting of toluene, xylene, benzene, and ethylbenzene;

Halogenated hydrocarbons selected from the group consisting of carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, and monochlorobenzene;

Ethers selected from the group consisting of tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol;

Dimethylformamide; Dimethylacetamide; Dimethyl sulfoxide; And sulfolane may be used alone or in combination of two or more thereof.

The solvent serves to dissolve, emulsify or disperse the photosensitive composition, the content of which is preferably included in 30 to 90% by weight of the total photosensitive resin composition.

3) The polyfunctional crosslinking agent is not particularly limited and may be appropriately selected and used depending on the intended purpose, and in order to improve the film strength after curing of the photosensitive layer formed using the photosensitive composition, without affecting developability or the like. Can be used. Examples of such polyfunctional crosslinking agents include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) ) Acrylate, trimethylol ethane triacrylate, trimethylolpropane triacrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetra acrylate, pentaerythritol triacrylate, dipentaerythritol penta acrylate, and At least one selected from the group consisting of dipentaerythritol hexa acrylate, but is not limited thereto.

Also, polyfunctional crosslinking agents incorporating caprolactone include KAYARAD DPCA-20, 30, 60, 120, and FA-2D, FA1DT, and FA-3 introduced in dipentaerythritol, and tetra 36-18 hydrofuryl acryl. KAYARAD TC-110S introduced to the rate, or KAYARAD HX-220 and KAYARAD HK-620 introduced to neopentyl glycol hydroxy pivalate. In addition, as the multifunctional crosslinking agent that can be used, at least one selected from U-324A, U15HA, and U-4HA may be used as an epoxy acrylate, a novolak-epoxy acrylate of a bisphenol A derivative, or a urethane-based multifunctional acrylate.

The content of the multifunctional crosslinking agent is preferably included in 1 to 30% by weight of the total photosensitive resin composition.

4) Photoinitiator of the present invention is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6- Triazine, 2,4-trichloromethyl- (pipelonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- { Triazine compounds such as 4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid;

Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5'-tetraphenylbiimidazole;

2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetophenone-based compounds (Irgacure- such as polyno-1-propane-1-one (Irgacure-907) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one) 369);

O-acyl oxime compounds such as Ciba geigy's Irgacure OXE 01, CGI-242, benzophenones such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone compound;

Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone and diisopropylthioxanthone;

2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as these; and

3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] At least one compound selected from coumarin-based compounds such as -benzopyrano [6,7,8-ij] -quinolizine-11-one, the content of which is usually sufficient to be included.

5) As the coloring pigment, it can be appropriately selected and used according to the color of the desired matrix. In particular, the black matrix uses carbon black as the coloring pigment, but its content and type are not limited thereto.

In addition to the above-mentioned compositions, other components such as surfactants, fillers, antifoaming agents, flame retardants, antioxidants and the like can be used in combination within the scope of not deteriorating the physical properties of the photosensitive composition desired in the present invention, and specific examples thereof are usually used. If used, it is not limited.

The photosensitive layer using the photosensitive resin composition having the composition described above is formed by applying the composition using conventional methods such as spin coating, slit spin coating, roll coating, die coating, curtain coating, and the like through exposure and development processes. Let's do it. Exposure and development processes also use the method used at the time of forming the photosensitive layer using a normal photosensitive resin composition, and are not specifically limited.

In the said exposure process, there is no restriction | limiting in particular as light irradiated from the said light irradiation means, Although it can select suitably according to the objective, Visible light, an electron beam, an X-ray, a laser beam etc. are mentioned from an electromagnetic wave and ultraviolet.

The method of irradiating light by the light irradiating means is not particularly limited and may be appropriately selected in accordance with the purpose. Examples of the method include high pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, cold cathode tubes for radiators, For example, by a known light source.

The said developing process is a process of exposing the said photosensitive layer by the said exposure process, hardening the exposed area | region of the said photosensitive layer, and developing by removing an uncured area | region, and forming a permanent pattern.

The developing solution is not particularly limited and may be appropriately selected according to the purpose. Examples of the developing solution include a hydroxide or carbonate of an alkali metal or an alkaline earth metal, a hydrogen carbonate, an aqueous ammonia solution and an aqueous solution of a quaternary ammonium salt. Among these, an aqueous sodium carbonate solution is particularly preferable.

The developer may be a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.); In order to promote the development, an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. The developing solution may be an aqueous developing solution obtained by mixing water or an alkali aqueous solution with an organic solvent, or may be an organic solvent alone.

The thickness of the photosensitive layer of the present invention may vary depending on the purpose, preferably 1 to 5 ㎛.

 Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Synthesis Example 1 <Synthesis of Hyper Branch Resin Polymer>

In a 250 ml three-neck flask, 27.08 g of bisphenol A glycidyl ether diacrylate (molecular weight = 484.55), 1.34 g of trimetholpropane (molecular weight = 120.15), and 6.58 g of hexamethylene diisocyanate (molecular weight = 168.20) were dissolved in propylene glycol. To 65.00 ml of methyl ether acetate, 0.3 g of N, N-dimethylaminopyridine (molecular weight = 122.17) was added as a catalyst, stirred for 10 hours under reflux of the solvent, and reacted to produce a urethane bond. Then, 6.71 g of succinic anhydride (molecular weight 100.07) was added and reacted for further 5 hours to obtain 107 g of a polymer including an acid group.

The acid value of the said polymer resin was 90 mgKOH / g. The polystyrene reduced weight average molecular weight measured by GPC was 8,000 g / mol.

Synthesis results of the polymer were confirmed by NMR. (Fig. 1)

Synthesis Example 2 <Synthesis of Hyper Branch Resin Polymer>

27.08 g of bisphenol A glycidyl ether diacrylate (molecular weight = 484.55), 1.47 g of 1,3,5-cyclohexanetriol (molecular weight = 132.08) in a 250 ml three-necked flask, hexamethylene diisocyanate (molecular weight = 168.20) 6.58 g was added to 65.00 ml of solvent propylene glycol methyl ether acetate, 0.3 g of N, N-dimethylaminopyridine (molecular weight = 122.17) was added as a catalyst, stirred for 10 hours under reflux of the solvent, and reacted to form a urethane bond. I was. Then, 6.71 g of succinic anhydride (molecular weight 100.07) was added and reacted for further 5 hours to obtain 107 g of a polymer including an acid group.

The acid value of the said polymer resin was 85 mgKOH / g. The polystyrene reduced weight average molecular weight measured by GPC was 9,500 g / mol.

Synthesis results of the polymer were confirmed by NMR. (Figure 2)

Comparative Synthesis Example 1 <Synthesis of Existing Urethane-Based Binder>

To a 250 ml three-necked flask, 28.16 g of bisphenol A glycidyl ether diacrylate (molecular weight = 484.55) and 6.84 g of hexamethylene diisocyanate (molecular weight = 168.20) were added to 65.00 ml of solvent propylene glycol methyl ether acetate, followed by catalyst 0.3 g of N, N-dimethylaminopyridine (molecular weight = 122.17) was added thereto, stirred for 10 hours under reflux of the solvent, and reacted to produce a urethane bond. Then, 7.08 g of succinic anhydride (molecular weight 100.07) was added, and the mixture was further reacted for 5 hours to obtain 108 g of a polymer including an acid group.

The acid value of the said polymer resin was 99 mgKOH / g. The polystyrene reduced weight average molecular weight measured by GPC was 9,700 g / mol.

Synthesis results of the polymer were confirmed by NMR. (Fig. 3)

Example 1

20 g of the hyperbranched resin polymer obtained in Synthesis Example 1, 10 g of the polyfunctional crosslinking agent dipentaerythritol hexa acrylate (DPHA), 50 g of colored pigment carbon black, 3.0 g of a photoinitiator, and 1 g of a surfactant were dissolved in 50 g of a solvent PGMEA, and thus photosensitive resin. The composition was prepared.

The composition was applied to a glass substrate by spin coating to have a film thickness of 1.0 μm, and dried in an oven at 80 ° C. for 30 minutes to form a photosensitive layer. Then, it was irradiated and exposed so as to obtain a desired wiring pattern using a laser beam having a wavelength of 405 nm, followed by spray development (spray pressure: 2.0 kgf / cm 2) for 60 seconds using a 1% by weight aqueous solution of sodium carbonate. The unexposed part was removed.

Example 2

Except for using the hyperbranched resin polymer obtained in Synthesis Example 2, a photosensitive resin composition was prepared in the same manner as in Example 1, to form a photosensitive layer.

Comparative Example 1

Except for using the hyperbranched resin polymer obtained in Comparative Synthesis Example 1, a photosensitive resin composition was prepared in the same manner as in Example 1, to form a photosensitive layer.

<Experimental Example>

<Phenomena Evaluation Experiment>

The photosensitive resin compositions of Examples 1 and 2 and Comparative Example 1 were filtered using a 5 micron filter. After spin coating on the glass substrate and electrothermal treatment at about 100 ° C. for 2 minutes, forming a uniform film having a thickness of about 2.5 μm, and exposing, measuring the time at which the pattern began to appear on the entire glass substrate. It was. The evaluation results are shown in Table 1.

Develop time (seconds) Example 1 7 Example 2 9 Comparative Example 1 13

<Viscosity measurement>

The average value which measured the photosensitive resin composition of Example 1, Example 2, and the comparative example 1 using the vibro viscometer SV-10 of AND company 3 times is shown in Table 2.

Viscosity (cp) Example 1 3.9 Example 2 4.0 Comparative Example 1 4.3

<Sensitivity>

Sensitivity is developed by coating each PR composition on CrBM and developing after exposure for each exposure in the range of 20 ~ 80mJ / cm2 with a 90µm width pattern mask to determine the thickness and CD (Pritical dimension) of the PR pattern after PB. Observation of the result is shown in Table 3.

Exposure amount (mJ / cm2) Thickness (㎛) CD (μm) Example 1 20 1.410 106 40 1.464 111 60 1.481 113 80 1.466 111 Example 2 20 1.488 107 40 1.468 109 60 1.512 109 80 1.502 111 Comparative Example 1 20 1.432 105 40 1.485 109 60 1.467 107 80 1.511 104

In the case of Examples 1 and 2 as described above, despite the lower acid value compared to the composition of the comparative example, developability is improved by 4 seconds or more, and the viscosity was reduced by 0.3cp or more. As a result of the thickness and the CD, it was confirmed that the urethane binder had the same level of sensitivity or higher.

1 is a graph showing the NMR results of the resin polymer prepared in Synthesis Example 1 according to the present invention.

Figure 2 is a graph showing the NMR results of the resin polymer prepared in Synthesis Example 2 according to the present invention.

Figure 3 is a graph showing the NMR results of the resin polymer prepared in Comparative Synthesis Example 1 according to the present invention.

Claims (13)

A hyperbranched polymer produced by the reaction of compounds represented by the following formula (1) to (4). [Formula 1]

Wherein R ₁ is

(Z is either a direct bond or selected from C ₁ to C ₆ alkylene), R ₂ is selected from hydrogen or methyl, and R ₃ is each independently selected from hydrogen or an alkyl group of C ₁ -C ₄ One.) [Formula 2]

(Wherein R ₄ is C ₁ -C ₈ alkyl, R ₅ is C ₁ -C ₈ alkyl and R ₆ is directly connected or C ₁ -C ₈ alkylene.) (3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene. [Formula 4]

Wherein R ₈ and R ₉ are each C ₁ -C ₁₀ alkyl. The method of claim 1, The compound represented by the formula (4) is a hyperbranched polymer, characterized in that succinic anhydride, glutaric anhydride, or methyl succinic anhydride. The method of claim 1, The hyperbranched polymer, characterized in that the weight average molecular weight of the hyperbranched polymer is 1000 ~ 50000g / mol. Reacting a compound represented by Formula 1 with a compound represented by Formula 2 with a compound represented by Formula 3 in a solvent to generate a urethane bond; And Reacting by adding a compound represented by the following formula (4) to the reactant Method for producing a hyperbranched polymer comprising a. [Formula 1]

Wherein R ₁ is

(Z is either a direct bond or selected from C ₁ to C ₆ alkylene), R ₂ is selected from hydrogen or methyl, and R ₃ is each independently selected from hydrogen or an alkyl group of C ₁ -C ₄ One.) [Formula 2]

(Wherein R ₄ is C ₁ -C ₈ alkyl, R ₅ is C ₁ -C ₈ alkyl and R ₆ is directly connected or C ₁ -C ₈ alkylene.) (3)

Wherein R ₇ is C ₁ to C ₁₀ alkylene. [Formula 4]

Wherein R ₈ and R ₉ are each C ₁ -C ₁₀ alkyl. The method of claim 4, wherein the content ratio of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is 1.0: 0.05 to 1.0: 0.7. The hyperbranched polymer according to claim 4, wherein the equivalent ratio of the mixture of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 is 1.0: 0.5 to 1.0: 0.99. Manufacturing method. 5. The method of claim 4, Compound represented by the formula (4) is trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethyl hexamethylene diisocyanate Method for producing a hyperbranched polymer. The photosensitive resin composition containing the hyperbranched polymer of any one of Claims 1-3, a solvent, a polyfunctional crosslinking agent, a photoinitiator, and a coloring pigment. 9. The method of claim 8, The content of the hyperbranched polymer is a photosensitive resin composition, characterized in that 1 to 20% by weight based on the total photosensitive resin composition. 9. The method of claim 8, The solvent is methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, ethyl acetate, acetic acid Butyl, n-amyl acetate, methyl sulfate, ethyl propionate, methyl phthalate, ethyl benzoate, methoxypropyl acetate, toluene, xylene, benzene, ethylbenzene, carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloro Ethane, methylene chloride, monochlorobenzene, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, Or sulfolane. 9. The method of claim 8, The polyfunctional crosslinking agent is polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, Trimethylol ethane triacrylate, trimethylolpropane triacrylate, neopentylglycol (meth) acrylate, pentaerythritol tetra acrylate, pentaerythritol triacrylate, dipentaerythritol penta acrylate, or dipentaerythritol It is hexa acrylate, The photosensitive resin composition characterized by the above-mentioned. 9. The method of claim 8, Examples of the photoinitiator include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2 , 4-trichloromethyl- (piflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2 , 4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl Biimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, 1- Hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one (Irgacure-907) , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O-acyl oxime compound, 4,4'-bis (dimethyla No) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone, diisopropyl thioxanthone, 2 , 4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichlorobenzoyl) propyl phosphine oxide, 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin, or 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl ] -Benzopyrano [6,7,8-ij] -quinolizine-11-one. The photosensitive resin composition characterized by the above-mentioned. 9. The method of claim 8, The photosensitive resin composition further comprises a surfactant, a filler, an antifoaming agent, a flame retardant, an antioxidant or a mixture thereof.

Images