JPH11228639A - Cellulose derivative compound and ultraviolet light-curable resin composition and solder-resist photoink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of preparing solder-resist photoinks capable of being developed with diluted alkali aqueous solutions by reacting a cellulose derivative having a carboxyl group with an ethylenic unsaturated monomer having an epoxy group and a polybasic acid anhydride. SOLUTION: This cellulose derivative compound is obtained by reacting a cellulose derivative having a carboxyl group [for example, a compound of the formula (R is H, CH3 , COCH3 or the like)] with an ethylenic unsaturated monomer having an epoxy group in the molecule (for example, glycidyl acrylate or glycidyl methacrylate) in the presence of a thermal polymerization inhibitor (for example, hydroquinone, hydroquinone monomethyl ether) and a catalyst (for example, benzyldimethylamine or triethylamine) in a solvent preferably at 80-120 deg.C under agitation and subsequently subjecting the reaction product to an addition reaction with a saturated or unsaturated polybasic acid anhydride (for example, succinic anhydride or methylsuccinic anhydride).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cellulose derivative compound having both an ethylenically unsaturated group and a carboxyl group. Further, the present invention is an ultraviolet-curable resin composition that can be developed with a dilute alkaline aqueous solution containing the above-mentioned cellulose derivative-based compound, and includes a resist ink for manufacturing a printed wiring board such as an etching resist ink and a plating resist ink, and The present invention relates to a filter suitably used for a protective film of a color filter and an image element. This ultraviolet curable resin composition is most suitable as a photo solder resist ink suitably used for manufacturing a printed wiring board having a fine and high-density conductor pattern.

[0002]

2. Description of the Related Art In order to cope with finer and higher-density conductor patterns of various types of printed wiring boards for consumer and industrial use, a developable liquid material having excellent resolution and dimensional accuracy is also used in forming a solder resist. Photoresist inks and the like are preferably used. As this liquid photo solder resist ink, for example, as disclosed in JP-A-61-243869, generally, a UV curable resin, a photopolymerization initiator and an epoxy compound soluble in a dilute aqueous alkali solution are used. What can be developed with a diluted alkaline aqueous solution is used.

[0003] A sufficient amount of carboxyl groups is introduced into the above-mentioned ultraviolet curable resin to enable development with an aqueous alkali solution. In addition, the thermosetting epoxy compound compounded in these inks increases the crosslink density of the solder resist by polymerization or reaction with carboxyl groups present in the solder resist, thereby forming a finally formed solder resist. It has the effect of thermally and chemically stabilizing.

[0004]

However, when an epoxy compound is blended in the resist ink, thermal curing due to reaction with a carboxyl group present in an ultraviolet curable resin or the like occurs even under predrying conditions. ,
Poor development and poor resolution in the development process were likely to occur. For this reason, the amount of the epoxy compound used is limited to a range that does not cause these problems, and there is a certain limit in improving the physical properties of the formed resist such as heat resistance and electric corrosion resistance. Therefore, at present, liquid photo-solder resist inks that can be developed with a dilute alkaline aqueous solution are slightly inferior in physical properties such as solder heat resistance and electric corrosion resistance as compared with conventionally used thermosetting solder resists. These improvements have been desired.

The present invention has been made in view of the above points, and has excellent resolution, sensitivity, soldering heat resistance, etc., and excellent substrate adhesion, chemical resistance, electrolytic corrosion resistance and electrical characteristics, and particularly, Cellulose derivative-based compound capable of preparing a photo solder resist ink developable with a dilute alkaline aqueous solution capable of forming a solder resist exhibiting excellent solder heat resistance on a substrate, and an ultraviolet curable resin using the same It is intended to provide a composition.

The present invention also provides a solder resist which is excellent in resolution, sensitivity, solder heat resistance and the like, and has excellent substrate adhesion, chemical resistance, electric corrosion resistance and electric properties, and particularly excellent solder heat resistance. It is an object of the present invention to provide a photo solder resist ink which can be developed with a dilute alkaline aqueous solution and which can be formed on a substrate.

[0007]

Means for Solving the Problems The cellulose derivative compound (A) according to claim 1 of the present invention is characterized in that a cellulose derivative (a) having a carboxyl group is added to an ethylenic derivative having one epoxy group in the molecule. It is produced by reacting a saturated monomer (b) with a saturated or unsaturated polybasic acid anhydride (c), and has both ultraviolet curability and alkali solubility. Further, this cellulose derivative-based compound (A) is excellent in flexibility, and is presumed to be provided by a cellulose skeleton.

Further, the ultraviolet curable resin composition according to the second aspect of the present invention is characterized in that (A) a cellulose derivative having a carboxyl group (a) is added to an ethylenically unsaturated monomer having one epoxy group in a molecule. Derivative-based compound produced by reacting the monomer (b) with a saturated or unsaturated polybasic acid anhydride (c) (B) an ultraviolet-curable resin composition having an ethylenically unsaturated bond (D) light It is characterized by comprising a polymerization initiator (E) a diluent, and containing a cellulose derivative compound (A) and an ultraviolet curable resin composition (B) to adjust photocurability, In addition, the physical properties of the cured film can be adjusted.

The ultraviolet-curable resin composition according to claim 3 of the present invention is characterized in that (A) a cellulose derivative having a carboxyl group (a) is added to an ethylenically unsaturated monomer having one epoxy group in a molecule. Cellulose derivative-based compound produced by reacting the compound (b) with a saturated or unsaturated polybasic acid anhydride (c), (C) a polyfunctional epoxy compound, (D) a photopolymerization initiator, and (E) a diluent. By containing a cellulose derivative-based compound (A) imparted with flexibility, the cured film formed has flexibility, hardness, heat resistance, and It can provide excellent adhesion.

The ultraviolet-curable resin composition according to claim 4 of the present invention is characterized in that (A) a cellulose derivative having a carboxyl group (a) is added to an ethylenically unsaturated monomer having one epoxy group in a molecule. Cellulose derivative-based compound produced by reacting the compound (b) with a saturated or unsaturated polybasic acid anhydride (c) (B) UV-curable resin having an ethylenically unsaturated bond (C) Polyfunctional epoxy compound (D) a photopolymerization initiator, (E) a diluent, and a combination of a cellulose derivative compound (A) imparted with flexibility and an ultraviolet curable resin (B). By doing so, the cured film to be formed can have excellent flexibility, hardness, heat resistance, and adhesion to a substrate, and can have excellent resolution and developability.

[0011] The ultraviolet-curable resin composition according to claim 5 of the present invention further comprises, in addition to the constitution of claim 2 or 4,
(B) The ultraviolet curable resin having an ethylenically unsaturated bond has an acid value of 25 to 150 mgKOH / g. The photoresist ink according to claim 6 is made of the ultraviolet-curable resin composition according to any one of claims 2 to 4, and is used as an ink for manufacturing a printed wiring board for covering an edge portion of a circuit. It is excellent and can improve the physical properties such as adhesion, sensitivity, and solder heat resistance of the solder resist formed thereby.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The cellulose derivative-based compound (A) of the present invention is obtained by adding a cellulose derivative (a) having a carboxyl group to an unsaturated monomer (b) having one epoxy group in a molecule, It is obtained by reacting an unsaturated polybasic acid anhydride (c). The cellulose derivative having a carboxyl group as the component (a) is not particularly limited, and examples thereof include those represented by the following general formula.

[0013]

Embedded image

Depending on the combination of R, for example, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, cellulose acetate hexahydrophthalate, hydroxypropylmethylcellulose acetate phthalate, hydroxypropylmethylcellulose hexahydrophthalate and the like can be mentioned. Or in combination.

The ethylenically unsaturated monomer having one epoxy group in the molecule of the component (b) can be added to the above-mentioned cellulose derivative (a) having a carboxyl group in the presence of the ethylenically unsaturated monomer having one epoxy group in the molecule. By adding a saturated monomer, it is blended for the purpose of imparting photocurability due to an ethylenically unsaturated double bond. Therefore, the photocurability of the cellulose derivative-based compound (A) is directly controlled by the content of the structural unit derived from the ethylenically unsaturated monomer (b) having one epoxy group in the molecule. In addition, it is not preferable that the ethylenically unsaturated monomer (b) has two or more epoxy groups because the cellulose derivative compound may be polymerized.

Examples of the ethylenically unsaturated monomer (b) having one epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, (3,4-
Epoxycyclohexyl) methyl acrylate, (3,
Epoxycyclohexyl derivatives of acrylic acid or methacrylic acid such as 4-epoxycyclohexyl) methyl methacrylate, alicyclic epoxy derivatives of acrylate or methacrylate, and β-methylglycidyl acrylate or β-methylglycidyl methacrylate. They can be used alone or in combination. In particular, it is preferable to use glycidyl acrylate or glycidyl methacrylate which is widely used and easily available.

The above-mentioned saturated or unsaturated polybasic acid anhydride (c) is used mainly for giving an acid value to the cellulose derivative compound (A) and for redispersion and resolubility with a dilute alkali solution. Is done. The amount of the cellulose derivative compound (A) obtained by adding the saturated or unsaturated polybasic acid anhydride (c) is 25 to 150.
It is preferable to select the amount to be in the range of mgKOH / g. When the acid value is less than 25, the developability becomes poor. When the acid value is more than 150, the electric properties, electric corrosion resistance and water resistance of the solder resist to be formed due to the residual carboxyl groups in the resist after thermosetting. And the like. In addition, especially when an acid value is 40-100 mgKOH /
When the value is g, the optimum effect is obtained.

Examples of the saturated or unsaturated polybasic acid anhydride (c) include succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, Dibasic anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride Acid anhydrides such as acids and tribasic acids or more such as methylcyclohexenetetracarboxylic anhydride can be used, and these can be used alone or in combination.

The above addition reaction of the ethylenically unsaturated monomer (b) having one epoxy group in the molecule and the saturated or unsaturated polybasic acid anhydride (c) can be carried out, for example, as follows. it can. First, a cellulose derivative (a) having a carboxyl group is dissolved in a solvent that does not react with the ethylenically unsaturated monomer (b) having one epoxy group in the molecule and a saturated or unsaturated polybasic anhydride (c). Then, to the solution of the cellulose derivative (a) having a carboxyl group, an ethylenically unsaturated monomer (b) having one epoxy group in the molecule is added, and hydroquinone or hydroquinone monomethyl ether is used as a thermal polymerization inhibitor. As a catalyst, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, and triphenylstibine, etc. are added and mixed by stirring. ~ 150 ° C, particularly preferably It is reacted at a reaction temperature of 0 to 120 ° C.. Next, a saturated or unsaturated polybasic acid anhydride (c) is added thereto, and the addition reaction is carried out in the same manner as described above.

UV curable resin (B) used in the present invention
Although it is not particularly limited, for example, the following known ultraviolet curable resins can be used. (1) Polyfunctional epoxy compounds having at least two epoxy groups, for example, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin, tris (hydroxyphenyl) methane base Ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and unsaturated or saturated polybasic anhydrides such as succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Those obtained by adding phthalic anhydride or the like.

(2) A copolymer of an unsaturated polybasic anhydride such as maleic anhydride with an aromatic hydrocarbon having a vinyl group such as styrene or vinyl alkyl ether, for example, 2-hydroxyethyl (meth) In the molecule, such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, dibutylene glycol mono (meth) acrylate, etc. And a compound having one hydroxyl group and one photoreactive ethylenically unsaturated group.

(3) Ethylenically unsaturated monomers having no carboxyl group, for example, ethylene glycol ester (meth) acrylates such as alkyl (meth) acrylate, hydroxyethyl (meth) acrylate, and methoxyethyl (meth) acrylate And a carboxyl group, such as (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, etc. A compound obtained by reacting an ethylenically unsaturated compound having the compound, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, or the like.

(4) Ethylenically unsaturated monomers having an epoxy group, for example, glycidyl (meth) acrylate, 2
-Methylglycidyl (meth) acrylate, (3,4-
Polymers or copolymers containing (epoxycyclohexyl) methyl (meth) acrylate or the like as polymerized units may be added to ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid or the like and unsaturated or saturated polybasic acid anhydrides such as anhydride Those obtained by adding succinic acid, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.

The acid value of the ultraviolet-curable resin (B) is from 25 to 150 mgKOH / g in order to ensure good developability of the ultraviolet-curable resin composition of the present invention with a dilute alkali solution.
The ultraviolet curable resin composition of the present invention, which is preferably a cellulose derivative compound (A) as a resin component
Can be used alone or in combination with the ultraviolet curable resin (B). In this case, the sum of the amounts of the cellulose derivative compound (A) and the ultraviolet curable resin (B) used ensures good sensitivity and working characteristics of the ink and good physical properties of the finally formed resist. for,
It is desirable that the content be 10 to 80% by weight in the total amount of the ink components excluding the organic solvent in the diluent (E) to be mixed at the same time. The mixing ratio of the cellulose derivative compound (A) and the ultraviolet curable resin (B) is A: B = 100: 0 to 1:
It is desirably 99.

When the polyfunctional epoxy resin (C) is blended with the ultraviolet-curable resin composition of the present invention, the polyfunctional epoxy resin (C) may be a poorly solvent-soluble epoxy compound, a general-purpose solvent-soluble epoxy compound, or the like. Examples thereof include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol A-novolak epoxy resin, bisphenol F epoxy resin, triglycidyl isocyanurate, and YX4000 (oiled shell epoxy resin). Sorbitol polyglycidyl ether, N-glycidyl type epoxy resin, alicyclic epoxy resin (for example, "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd.), polyol polyglycidyl ether compound, glycidyl ester compound, N- Rishijiru type epoxy resins, tris (hydroxyphenyl) methane-based polyfunctional epoxy resin (Nippon Kayaku Co., Ltd. EPPN-502H, and Dow Chemical Co. Tactile tex -742 and XD-9053
Etc.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene-phenol type epoxy resin, naphthalene type epoxy resin, vinyl polymer having epoxy group and the like, and these can be used alone or in combination. Particularly, triglycidyl isocyanurate, YX4000, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol A-novolak type epoxy resin and the like are desirable.

The compounding amount of the polyfunctional epoxy resin (C) in the resist ink is determined by adjusting the amount of the diluent (E) to be mixed together.
0.1 to 5 in the total amount of the ink components excluding the organic solvent therein
It is preferably 0% by weight, and an optimum effect can be obtained particularly in the range of 0.1 to 30% by weight. Examples of the photopolymerization initiator (D) include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, and alkyl ethers thereof, acetophenone, and 2,2-dimethoxy-2.
-Phenylacetophenone, 2,2-diethoxy-2-
Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methylanthraquinone;
Anthraquinones such as 2-amylanthraquinone, and thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and 1-chloro-4-propoxythioxanthone; and Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ′, 4,4 ′
-Benzophenones or xanthones such as tetra- (t-butylperoxylcarbonyl) benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, and 2-methyl-1- [4- (methylthio) phenyl]-
Those containing a nitrogen atom such as 2-morpholino-propan-1-one, 2-benzoyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4,4′-bis-diethylaminobenzophenone, And 2,
And tertiary amines such as benzoic acid-based or p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 2-dimethylaminoethylbenzoate. You may use together with well-known photopolymerization accelerators, sensitizers, etc., such as a system. These photopolymerization initiators are blended alone or in combination with one another as appropriate.

For example, as a sensitizer for laser exposure, 7
Coumarin derivatives such as -diethylamino-4-methylcoumarin, 4,6-diethyl-7-ethylaminocoumarin,
Other carbocyanine dyes, xanthene dyes and the like can also be appropriately selected, and the ultraviolet-curable resin composition of the present invention can be made visible or near-infrared curable. To the extent possible, those using these are also included. The compounding amount of the photopolymerization initiator (D) in the ultraviolet-curable resin composition is adjusted so as to obtain a good balance between the photocurability and the physical properties of the obtained ultraviolet-curable resin composition. The content is preferably 0.1 to 30% by weight based on the total amount of the ink components excluding the organic solvent in E).

As the diluent (E), a photopolymerizable monomer or an organic solvent can be used alone or in combination.
Examples of the photopolymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, (meth) acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, Methoxy polyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth)
Acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, melamine (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobonyl (meth) acrylate, cyclopentanyl mono (meth) acrylate, cyclopentenyl mono (meth)
Acrylates, cyclopentanyl di (meth) acrylates, cyclopentenyl di (meth) acrylates, and mono-, di-, tri- or higher polyesters of polybasic acids and hydroxyalkyl (meth) acrylates,
And (meth) acrylate monomers such as polyester (meth) acrylate and urethane (meth) acrylate. The photopolymerizable monomers can be used alone or in combination with one another as appropriate.

Examples of the organic solvent include linear, branched, secondary and polyhydric alcohols such as ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butyl alcohol, hexanol and ethylene glycol. , And methyl ethyl ketone, ketones such as cyclohexanone,
And aromatic hydrocarbons such as toluene and xylene; petroleum-based aromatic mixed solvents such as Swazol series (manufactured by Maruzen Petrochemical) and Solvesso series (manufactured by Exxon Chemical Company); and cellosolves such as cellosolve and butyl cellosolve. And carbitols such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; and polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; and ethyl acetate, butyl acetate, and cellosolve acetate. Acetic acid esters, such as butyl cellosolve acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ethers. Germany or in combination with one another as appropriate can be used.

The photopolymerizable monomer is prepared by diluting a cellulose derivative compound (A), an ultraviolet curable resin (B), etc.
It is easy to apply and adjusts the acid value to give photopolymerizability. The organic solvent dissolves and dilutes the cellulose derivative compound (A) and the ultraviolet curable resin (B),
It can be applied as a liquid and is formed into a film by drying.

The photopolymerizable component such as a photopolymerizable monomer as the diluent (E) is not necessarily required to be added to the resist ink. E) is desirably 50% by weight or less based on the total amount of the ink components excluding the organic solvent similarly formulated. If it is added in an amount exceeding 50% by weight, the surface tackiness of the dried coating film becomes too strong, and when a negative mask on which a pattern is drawn is directly applied to the dried coating film surface and exposed, the negative mask becomes stained. Prone to problems.

On the other hand, an organic solvent used as a diluent (E), like the above-mentioned photopolymerizable monomer, is an essential component of a photo solder resist ink which can be developed with a dilute alkaline solution of the present invention. It must be selected so that it will not volatilize and remain in the dried coating film. The amount of the organic solvent in the resist ink is 5% in the total amount of the ink components.
% Is desirable, and if it is less than this, it tends to be difficult to apply the ink. Since the preferred amount varies depending on the application method, it is necessary to appropriately adjust the amount according to the application method.

In addition to the above components, the photo solder resist ink of the present invention may further comprise, for example, tolylene diisocyanate, morpholine diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate blocked with caprolactam, oxime, malonic ester and the like. Isocyanate, and n-butylated melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea co-condensation resin, thermosetting components such as amino resins such as benzoguanamine-based co-condensation resin, and ultraviolet curable epoxy acrylate or UV-curable epoxy methacrylates such as bisphenol A type, phenol novolak type, cresol novolak type, epoxy resin such as alicyclic type to which acrylic acid or methacrylic acid is added, and Len - (meth) acrylic acid - (meth) acrylic acid ester copolymer, styrene - maleic acid resins, diallyl phthalate resins, phenoxy resins, melamine resins, urethane resins, can be added to a polymer compound such as a fluorine resin.

The resist ink may further contain an epoxy resin curing agent such as an imidazole derivative, a polyamine, a guanamine, a tertiary amine, a quaternary ammonium salt, a polyphenol, or a polybasic acid anhydride, if necessary. Hardening accelerators, fillers and coloring agents such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, etc., and leveling agents such as silicon and acrylate copolymers, fluorine-based surfactants, and silane coupling agents Adhesion promoter, a thixotropic agent such as Aerosil, and a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, an antihalation agent, a flame retardant, a defoaming agent,
Various additives such as an antioxidant and a surfactant or a polymer dispersant for improving the dispersion stability may be added.

The photo solder resist ink of the present invention is prepared, for example, by a known kneading method using three rolls, a ball mill, a sand mill, etc., for each compounding component and additives. The method for forming a resist pattern on a substrate using the resist ink is not particularly limited.
The most common method among them is as follows.

For example, after a resist ink is applied on a substrate by dipping, spraying, spin coater, roll coater, curtain coater, screen printing, or the like,
To volatilize an organic solvent as a diluent, for example, 60 to 1
Predry at 20 ° C. Next, a negative mask on which the pattern is drawn is applied directly or indirectly to the dried coating surface, and ultraviolet light is applied using a chemical lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a metal halide lamp. After the irradiation, a pattern is formed by development, and further, for example, at 120 to 180 ° C. for 30 minutes.
By curing the epoxy compound by heating for about 90 minutes, the film strength, hardness and chemical resistance of the resist are improved.

Examples of the alkaline solution used in the developing step include an aqueous solution of sodium carbonate and an aqueous solution of potassium carbonate. As the solvent for the alkaline solution, water or a mixture of water and a hydrophilic organic solvent such as an alcohol can be used.

[0038]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, "part" and "%" used below are all based on weight unless otherwise specified. Also, "weight average molecular weight"
Is a value measured by GPC based on the following measurement conditions.

A THF solution was prepared so that each sample had a solid content of 10 mg / milliliter, and each sample was measured at an injection volume of 100 microliter. Measurement conditions GPC measuring device: SHODEX SYSTEM 11 manufactured by Showa Denko Co., Ltd. Column: 4 series of SHODEX KF-800P, KF-805, KF-803 and KF-801 Moving bed: THF flow rate: 1 ml / min Column temperature: 45 ° C. Detector: RI Conversion: polystyrene [Synthesis Example 1] Hydroxypropyl methylcellulose acetate succinate (AS manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a stirrer.
-L) 40 parts, carbitol acetate 160 parts, hydroquinone 0.05 part, glycidyl methacrylate
7 parts and 0.2 parts of dimethylbenzylamine,
9.3 parts of tetrahydrophthalic anhydride and 14.8 parts of carbitol acetate were added thereto, and the mixture was reacted at 100 ° C. for 3 hours to give a 25% solution of a cellulose derivative compound (25% cellulose). A derivative compound (A-1) solution) was obtained.

The solvent of the above solution was removed to obtain a product (cellulose derivative compound (A-1)). FIG. 1 shows a GPC chart of the cellulose derivative compound (A-1), and FIG. 2 shows an infrared absorption spectrum of the cellulose derivative compound (A-1). GP of cellulose compound (A-1)
The weight average molecular weight of C peak 1 was 452,000, and the acid value was 59 mgKOH / g. The GPC was measured under the above conditions in all of the following synthesis examples, and the infrared absorption spectrum of the product was measured by the NaCl method. [Synthesis Example 2] Instead of glycidyl methacrylate, CY
A cellulose derivative-based compound was prepared in the same manner as in Synthesis Example 1 except that 12 parts of CLOMER M-100 (trade name, manufactured by Daicel Chemical Industries, Ltd.) and 9.5 parts of hexahydrophthalic anhydride were used instead of tetrahydrophthalic anhydride. Compound 25% solution (25% cellulose derivative compound (A-
2) A solution) was obtained.

The solvent of the above solution was removed to obtain a product (cellulose derivative compound (A-2)). FIG. 3 shows a GPC chart of the cellulose derivative compound (A-2), and FIG. 4 shows an infrared absorption spectrum of the cellulose derivative compound (A-2). Cellulose derivative compound (A-
The weight average molecular weight of GPC peak 1 in 2) was 268,00.
0, the acid value was 56 mgKOH / g. [Synthesis Example 3] Hydroxypropyl methylcellulose hexahydrophthalate (HPMCHHP manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hydroxypropylmethylcellulose acetate succinate, glycidyl methacrylate was 10.3 parts, tetrahydrophthalic anhydride was 11.0 parts, Except for adding 45 parts of carbitol acetate,
In the same manner as in Synthesis Example 1, a 25% solution of a cellulose derivative compound (25% cellulose derivative compound (A
-3) Solution) was obtained.

The solvent of the above solution was removed to obtain a product (cellulose derivative compound (A-3)). FIG. 5 shows a GPC chart of the cellulose derivative compound (A-3), and FIG. 6 shows an infrared absorption spectrum of the cellulose derivative compound (A-3). Cellulose derivative compound (A-
The weight average molecular weight of GPC peak 1 in 3) is 205,000
0, the acid value was 135 mgKOH / g. [Synthesis Example 4] In a four-necked flask equipped with a reflux condenser, a thermometer, a glass tube for introducing nitrogen, and a stirrer, 70 parts of glycidyl methacrylate, 10 parts of methyl methacrylate,
20 parts of t-butyl methacrylate, 100 parts of carbitol acetate, 0.3 part of lauryl mercaptan, and 3 parts of azobisisobutyronitrile were added, and the mixture was heated under a nitrogen stream, polymerized at 75 ° C. for 5 hours, and polymerized at 50% A copolymer solution was obtained.

To the above 50% copolymer solution were added 0.05 part of hydroquinone, 37 parts of acrylic acid and 0.2 parts of dimethylbenzylamine, and an addition reaction was carried out at 105 ° C. for 24 hours, followed by tetrahydrophthalic anhydride 38 parts. Parts and 72 parts of carbitol acetate were added and reacted at 100 ° C. for 3 hours to obtain a 50% UV-curable resin (B-1) solution having a weight average molecular weight of 22,000. Its acid value is 8
It was 0 mgKOH / g. [Synthesis Example 5] The same procedure as in Synthesis Example 4 was repeated, except that 5 parts of tetrahydrophthalic anhydride and 42 parts of carbitol acetate were added, to obtain a 50% powder having a weight average molecular weight of 23,000.
% UV curable resin (B-2) solution was obtained. Its acid value was 13 mgKOH / g. [Synthesis Example 6] A weight average molecular weight of 23,000 was obtained in the same manner as in Synthesis Example 4 except that 152 parts of tetrahydrophthalic anhydride and 190 parts of carbitol acetate were added.
Of a 50% ultraviolet curable resin (B-3) was obtained. Its acid value was 194 mgKOH / g. [Reference Example 1] In a four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, hydroxypropyl methylcellulose acetate succinate (AS manufactured by Shin-Etsu Chemical Co., Ltd.)
-L) 40 parts, carbitol acetate 150 parts, hydroquinone 0.05 part, glycidyl methacrylate
7 parts and 0.2 parts of dimethylbenzylamine,
Perform addition reaction at 15 ° C for 15 hours, and add 25%
A solution (25% cellulose resin (F-1) solution) was obtained.

The solutions of the cellulose derivative compounds (A-1) to (A-3), the UV curable resins (B-1) to (B-3), and the cellulose resin (F-1) produced in the above synthesis examples. ) An epoxy compound having two or more epoxy groups in one molecule was added to the solution at the compounding amount shown in Table 1 to prepare an ultraviolet curable resin composition (photosolder) of Examples 1 to 6 and Comparative Examples 1 to 3. Resist ink). In Table 1, “Epiclon N-695” (trade name) is a cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, and “Irgacure 907” (trade name) is a photopolymerization initiator manufactured by Ciba Geigy. Yes, and "Kayacure D
"ETX-S" (trade name) is a photopolymerization initiator manufactured by Nippon Kayaku, and "Modaflow" (trade name) is a leveling agent manufactured by Monsanto. “DPHA” is dipentaerythritol hexaacrylate.

[0045]

[Table 1]

[Evaluation of Performance of Resist Ink] -Remaining Step Stage- The resist inks of Examples 1 to 6 and Comparative Examples 1 to 3 are screened on the entire surface of a copper-clad laminate made of a 35-μm-thick copper foil glass epoxy substrate. Preliminary drying was performed under drying conditions of 80 ° C. and a drying time of 20 minutes in order to evaporate the solvent by printing, and test pieces having a dried coating film having a film thickness of 20 μm were prepared for each ink. Then ORC HM
W680GW (Oak Seisakusho's reduced pressure contact type double-sided exposure machine)
In step, a step tablet PHOTEC 21 step (exposure test mask manufactured by Hitachi Chemical Co., Ltd.) was directly applied to the dried coating film and brought into close contact with each other under reduced pressure.
Irradiation with ultraviolet light of cm ² was carried out, and then development was carried out using a 1% aqueous solution of sodium carbonate as a developing solution. [Evaluation of Performance of Printed Wiring Board] Next, in order to confirm the performance of the printed wiring board manufactured with each resist ink, test pieces were prepared by sequentially performing the following steps (I) to (V). (I) <Coating step> A liquid photo solder resist ink is applied to the entire surface of a copper-clad laminate made of a 35-μm-thick copper foil glass epoxy base material and a pattern formed by etching the copper-clad laminate in advance. It was applied by screen printing to form a resist ink layer on the substrate surface. (II) <Preliminary drying step> After the coating step, preliminary drying was performed at 80 ° C for 20 minutes in order to volatilize the solvent in the resist ink layer on the substrate surface, and a dried coating film having a thickness of 20 µm was obtained. (III) <Exposure step> Thereafter, a mask on which a pattern is drawn is directly applied to the surface of the dried coating film, and at the same time, the resist film is irradiated with an optimum amount of ultraviolet light for each resist ink to selectively expose the dried coating film on the substrate surface. went. (IV) <Development step> In the dried coating film after the exposure step,
Selectively unexposed portions were removed by developing with a 1% aqueous solution of sodium carbonate as a developing solution to form a pattern of an exposed and cured dried coating film on the substrate. (V) <Post-baking step> The substrate on which the pattern of the exposed and cured dried coating film obtained in the developing step is formed is heated at 150 ° C for 30 minutes to cure the dried coating film.
I got a test piece.

The following evaluation was performed on the test pieces obtained in the above steps. -Resolution- The formation state of a pattern formed by a mask pattern composed of concentric circles each having a line width and a line interval of 40 μm was observed. The evaluation method of the resolution is as follows. ×: No pattern was formed. Δ: The pattern was formed, but a part thereof was missing. ：: A sharp pattern could be obtained. -Solder heat resistance-Using LONCO 3355-11 (water-soluble flux manufactured by London Chemical Company) as a flux, first apply a flux to a test piece, and then apply 260 ° C to the test piece.
Was then immersed in a molten solder bath for 15 seconds and then washed with water. After this cycle was performed once or five times, the degree of surface whitening was observed. In addition, a cellophane adhesive tape peeling test by cross cutting was performed in accordance with JIS D0202,
The change in the adhesion state was observed.

The evaluation method of surface whitening is as follows. ×: Remarkably whitened. Δ: Slight whitening was observed. ：: No abnormality occurred. The method for evaluating adhesion is as follows. X: The resist swelled or peeled off without performing a cross cut test. Δ: Partially peeled off at the cross cut portion during tape peeling. ：: No peeling of the cross cut portion occurred. -Other test items-Pencil hardness was measured and evaluated in accordance with JIS K 5400, and other items were evaluated by a common method.

[0049]

[Table 2]

As is clear from Table 2, Examples 1 to 6
In Examples, the resolution and the pencil hardness solder heat resistance were higher than those of Comparative Examples 1 to 3.

[0051]

As described above, the invention according to claim 1 of the present invention provides a cellulose derivative having a carboxyl group,
Since it is produced by reacting an ethylenically unsaturated monomer having one epoxy group in the molecule with a saturated or unsaturated polybasic acid anhydride, it has excellent resolution, sensitivity and solder heat resistance,
Also, a photo solder resist ink that can be developed with a dilute alkaline aqueous solution can be used to form a solder resist showing excellent substrate adhesion, chemical resistance, electrolytic corrosion resistance and electrical properties, and particularly excellent solder heat resistance on a substrate. It can be prepared.

The invention according to claims 2, 3, and 4 of the present invention provides a cellulose derivative-based compound according to claim 1,
Contains UV curable resin or polyfunctional epoxy compound with ethylenically unsaturated bond, photopolymerization initiator and diluent, so it has excellent resolution, sensitivity and soldering heat resistance, and excellent substrate adhesion It is possible to prepare a photo solder resist ink that can be developed with a dilute alkaline aqueous solution that can form a solder resist showing chemical resistance, chemical corrosion resistance, electrical properties, and particularly excellent solder heat resistance on a substrate. It is.

The invention according to claim 5 of the present invention is characterized in that the ultraviolet curable resin having an ethylenically unsaturated bond has an acid value of 2
Since it is 5 to 150 mgKOH / g, good developability with a dilute alkaline solution can be ensured. The invention according to claim 6 of the present invention is composed of the ultraviolet-curable resin composition according to any one of claims 2 to 5, and thus has excellent resolution, sensitivity, solder heat resistance, and the like, and also has excellent properties. And a solder resist exhibiting excellent substrate adhesion, chemical resistance, electrolytic corrosion resistance, electrical characteristics, and particularly excellent solder heat resistance.

[Brief description of the drawings]

FIG. 1 is a GPC chart of a cellulose derivative-based compound (A-1) produced in Synthesis Example 1 of the present invention. The peak indicated by the arrow is the peak 1, and the scale at the bottom represents the retention time (unit: minute).

FIG. 2 is a chart of an infrared absorption spectrum of the cellulose derivative compound (A-1) produced in Synthesis Example 1 of the present invention.

FIG. 3 is a GPC chart of a cellulose derivative-based compound (A-2) produced in Synthesis Example 2 of the present invention. The peak indicated by the arrow is the peak 1, and the scale at the bottom represents the retention time (unit: minute).

FIG. 4 is a chart of an infrared absorption spectrum of a cellulose derivative-based compound (A-2) produced in Synthesis Example 2 of the present invention.

FIG. 5 is a GPC chart of the cellulose derivative compound (A-3) produced in Synthesis Example 3 of the present invention. The peak indicated by the arrow is the peak 1, and the scale at the bottom represents the retention time (unit: minute).

FIG. 6 is a chart of an infrared absorption spectrum of a cellulose derivative-based compound (A-3) produced in Synthesis Example 3 of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 511 G03F 7/027 511 7/032 7/032 7/038 503 7/038 503

Claims (6)

[Claims] 1. It is produced by reacting a cellulose derivative having a carboxyl group with an ethylenically unsaturated monomer having one epoxy group in a molecule and a saturated or unsaturated polybasic acid anhydride. Cellulose derivative-based compound. 2. A resin produced by reacting (A) a cellulose derivative having a carboxyl group with an ethylenically unsaturated monomer having one epoxy group in the molecule and a saturated or unsaturated polybasic anhydride. An ultraviolet-curable resin composition comprising: (B) an ultraviolet-curable resin having an ethylenically unsaturated bond; (D) a photopolymerization initiator; and (E) a diluent. 3. A resin produced by reacting (A) a cellulose derivative having a carboxyl group with an ethylenically unsaturated monomer having one epoxy group in the molecule and a saturated or unsaturated polybasic anhydride. An ultraviolet-curable resin composition comprising a cellulose derivative compound (C) a polyfunctional epoxy compound (D) a photopolymerization initiator (E) a diluent. 4. A resin produced by reacting (A) a cellulose derivative having a carboxyl group with an ethylenically unsaturated monomer having one epoxy group in the molecule and a saturated or unsaturated polybasic anhydride. Cellulose derivative compound (B) UV curable resin having an ethylenically unsaturated bond (C) Polyfunctional epoxy compound (D) Photopolymerization initiator (E) Diluent Resin composition. 5. The ultraviolet-curable resin composition according to claim 2, wherein the acid value of the ultraviolet-curable resin (B) having an ethylenically unsaturated bond is 25 to 150 mgKOH / g. 6. A photo solder resist ink comprising the ultraviolet curable resin composition according to claim 2. Description: