JP2011225708A - Polyfunctional monomer, and resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyfunctional monomer characterized in that the monomer has low viscosity and low curing shrinkage despite high sensitivity.SOLUTION: The polyfunctional monomer (A) is obtained by esterifying pentaerythritol, dimethylol propionate and unsaturated monocarboxylic acid at one step. The resin composition including the above monomer solves the above problem.

Description

  The present invention relates to a polyfunctional monomer (A) obtained by esterifying pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid in one step. Further, an energy ray curable resin composition containing the polyfunctional monomer (A), a hard coat composition using the composition, a coating composition, a protective film composition, an energy ray curable resin composition, a photo The present invention relates to an ink composition such as a resist ink composition, an insulating layer composition, an adhesive and a cured product thereof, and further an article having the cured product.

  Photosensitive monomers with unsaturated groups are available in various structures ranging from monofunctional monomers to polyfunctional monomers, and are used in a wide range of fields, mainly paints, adhesives, and parts for electronic devices. .

  The properties required for photosensitive monomers include various things such as sensitivity, heat resistance, light resistance, moisture resistance, mechanical properties, transparency, and adhesiveness. Generally, highly sensitive polyfunctional monomers have high viscosity. In particular, improvement in curing shrinkage is desired when compared with thermosetting systems.

  In order to improve the property of low cure shrinkage, Patent Document 1 proposes a silphenylene compound having an oxirane ring structure.

  Patent Document 2 and Patent Document 3 propose a polymer obtained by reacting an initiator with a chain extender and then a chain terminator. When synthesizing the polymer, it is first obtained by reacting a chain extender with an initiator and further using a chain terminator in two or more stages. Therefore, the hydroxyl group of the initiator is extended by the chain extender, and the hydroxyl group of the chain extender reacts with the chain terminator to obtain a polymer.

JP 2004-323442 A JP 7-504219 A Special table 2000-511219 gazette

  An object of the present invention is to provide a polyfunctional monomer characterized by low viscosity and low cure shrinkage while being highly sensitive.

  The present inventor has found that the polyfunctional monomer (A) obtained by esterifying pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid in one step has a low viscosity and a low curing shrinkage while being highly sensitive. The present invention has been completed.

  One of the present inventions is a polyfunctional monomer (A) obtained by esterifying pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid in one step.

  One of the present invention is an energy ray curable resin composition containing the polyfunctional monomer (A). The resin composition may further contain a photopolymerization initiator.

  One aspect of the present invention is the resin composition used as a film forming material or an insulating material.

  One of the present invention is a cured product obtained by irradiating the resin composition with energy rays.

  One of the present invention is an article having the cured product.

  The polyfunctional monomer (A) of the present invention has a structure in which dimethylolpropionic acid and unsaturated monocarboxylic acid are reacted with the hydroxyl group of pentaerythritol and has high sensitivity and low curing shrinkage. The polyfunctional monomer (A) of the present invention is different from a polymer in which dimethylolpropionic acid is reacted with all hydroxyl groups of pentaerythritol and unsaturated monocarboxylic acid is reacted with hydroxyl groups of dimethylolpropionic acid. Does not stretch as much as molecules. Therefore, the resin composition of the present invention containing the polyfunctional monomer (A) of the present invention is suitable for a hard coat, coating, protective film, ink, insulating layer, adhesive, or photoresist ink.

  The polyfunctional monomer (A) of the present invention can be obtained by esterifying pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid in one step.

  When pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid are esterified in one step, the charging ratio of each raw material is not particularly limited, but the polyfunctional monomer (A) of the present invention can be changed by changing the charging ratio. Can be adjusted. For example, in order to most exhibit the characteristics of high sensitivity and low cure shrinkage in the polyfunctional monomer (A) of the present invention, dimethylolpropionic acid is usually 0.3 to 3.0 mol per mol of pentaerythritol. The equivalent amount of unsaturated monocarboxylic acid is usually about 4.3 to 7.0 molar equivalents. Preferably, 4.3 to 6.0 molar equivalents of unsaturated monocarboxylic acid and 0.3 to 2.0 molar equivalents of dimethylolpropionic acid are reacted with 1 equivalent of pentaerythritol, respectively. When the reaction amount of the unsaturated monocarboxylic acid is 4.3 to 6.0 molar equivalent, the sensitivity is excellent. When 2.0 to 3.0 molar equivalents of dimethylolpropionic acid are reacted with pentaerythritol, characteristics such as high sensitivity and low curing shrinkage can be obtained, but the viscosity of the polyfunctional monomer (A) of the present invention Slightly expensive. When dimethylolpropionic acid exceeding 3.0 molar equivalents is reacted with pentaerythritol, dimethylolpropionic acid has low solubility in a solvent, so that a polyfunctional monomer (A) can be obtained stably. It becomes difficult. When the reaction amount of dimethylolpropionic acid is less than 0.3 molar equivalent with respect to 1.0 equivalent of pentaerythritol, the sensitivity is lowered and the curing shrinkage is also increased.

  The unsaturated monocarboxylic acid is not particularly limited as long as it has an unsaturated bond in the molecule and can be esterified. Specific examples include acrylic acid, methacrylic acid, and those obtained by modifying these with caprolactone, but are not particularly limited thereto.

  In the synthesis of the polyfunctional monomer (A) of the present invention, a solvent is usually used, but the amount used may be appropriately adjusted depending on the usage, and one kind of solvent can be used alone, or two kinds can be used. The above can also be used in combination.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures thereof such as petroleum ether, white gasoline, Solvent naphtha etc. are mentioned.

  The solvent may be an ester solvent such as alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether monoacetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoacetate. Mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, dialkyl glutarate , Dialkyl succinate, dialkyl adipate, etc. Carboxylic acid alkyl ester and the like.

  The solvent may be an ether solvent, for example, alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene Examples include glycol ethers such as glycol diethyl ether and cyclic ethers such as tetrahydrofuran.

  The solvent may be a ketone solvent, and examples thereof include acetone, methyl ethyl ketone, cyclohexanone, isophorone and the like.

  During the esterification reaction, an acid catalyst may be used to promote the reaction. When the catalyst is used, the amount used is usually about 0.1 to 10% by mass with respect to the total amount of the reactants. The reaction temperature in that case is 60-150 degreeC normally, and reaction time is 5-60 hours normally.

  Examples of the catalyst include acid catalysts such as sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, but are not particularly limited as long as they are acid catalysts.

  Further, a thermal polymerization inhibitor may be used during the esterification reaction. Examples of the thermal polymerization inhibitor include hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, and 3,5-di-tert-butyl-4-hydroxytoluene.

  In the present invention, the energy ray curable resin composition indicates a material that is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The energy beam curable resin composition of the present invention is an energy beam curable resin composition containing the polyfunctional monomer (A) of the present invention. There is no special limitation in components other than the polyfunctional monomer (A) of this invention, and a component is suitably selected according to the objective.

  In the energy ray curable resin composition of the present invention, other components may be added up to 90% by mass in the resin composition. Other components include photopolymerization initiators, solvents, other monomers and oligomers, inorganic fillers, organic fillers, silane coupling agents, tackifiers, antifoaming agents, leveling agents, plasticizers and antioxidants. UV absorbers, flame retardants, dyes, and the like can be used as appropriate. Each of these other components can be used alone or in combination of two or more. Examples of other components that can be used are shown below.

  Specific examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- Acetophenones such as (methylthio) phenyl] -2-morpholino-propan-1-one; anthrax such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Nons; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  As the solvent, a solvent used in the synthesis of the polyfunctional monomer (A) of the present invention and other solvents can be used in the present invention. A solvent can also be used individually by 1 type and can also be used in combination of 2 or more types.

  The non-reactive compound that can be used in the present invention is a liquid or solid oligomer or resin having low reactivity or non-reactivity, and is a (meth) acrylic acid alkyl copolymer, liquid polybutadiene, dicyclopentadiene. Derivatives, saturated polyester oligomers, xylene resins, polyurethane polymers, ketone resins, diallyl phthalate polymers (dup resins), petroleum resins, rosin resins, fluorine-based oligomers, silicon-based oligomers, etc. is not.

  As the (meth) acrylic acid alkyl copolymer, the repeating unit contains an alkyl ester of (meth) acrylic acid or an acid type of (meth) acrylic acid. For example, degussa. Examples include Eudragit L100-55, Eudragit L100, Eudragit S100, and Plus Size L-8011 manufactured by Kyoyo Chemical Industry Co., Ltd.

  Examples of the saturated polyester oligomer include a polyester diol which is a reaction product of the above diol compound and the above dibasic acid or an anhydride thereof, and a reaction product of (meth) acrylic acid.

  Examples of the inorganic filler that can be used in the present invention include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate, magnesium carbonate, magnesium oxide, titanium oxide, zirconium oxide, talc, kaolin clay, calcined clay, zinc oxide, and sulfuric acid. Examples thereof include zinc, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, and glass balloon. These inorganic fillers may be added with a silane coupling agent, titanate coupling agent, aluminum coupling agent, zirconate coupling agent, or the like, and reacted to form a halogen group, an epoxy group, a hydroxyl group, or a thiol. It can also have a functional group.

  Examples of the organic filler that can be used in the present invention include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, and polymethyl methacrylate resin. , Fluororesin, nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, polyimide resin, and the like.

  Examples of the silane coupling agent that can be used in the present invention include silane coupling agents such as γ-glycidoxypropyl tremethoxysilane and γ-chloropropyltrimethoxysilane, and tetra (2,2-diallyloxymethyl-1). -Butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate coupling agents; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; zirconium cups such as acetylacetone / zirconium complexes Ring agents, and the like.

  Any tackifier, antifoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant, and dye that can be used in the present invention can be used as long as they are known and conventional. It can be used without particular limitation as long as the characteristics are not impaired.

  In order to obtain the energy beam curable resin composition of the present invention, the above-described components may be mixed, and the order and method of mixing are not particularly limited.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating and optical discs. Other examples include adhesive materials such as various adhesives and pressure-sensitive adhesives, resist inks used for photoresists, solder resists, etching resists, resists for micromachines, protective films, and the like. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

  In the present invention, the insulating material means that a film layer of the composition is formed on a base material, and an electric current flows even if a large electric resistance is applied between two target locations in an electronic circuit or its components. It refers to an energy ray curable resin composition that is in a non-existent state. Specific applications include overcoat materials for flexible wiring boards and interlayer insulation films for multilayer substrates, molding materials for insulation films and passivation films for solid elements in the semiconductor industry, and interlayers for semiconductor integrated circuits and multilayer printed wiring boards. It is also preferably used for an insulating material, a solder resist used for protecting the substrate, and the like.

  When the energy ray curable resin composition of the present invention is used as a film forming material or an insulating material, various coating films are formed. The method for forming this coating film is not particularly limited, but intaglio printing methods such as gravure, relief printing methods such as flexo, stencil printing methods such as silk screen, lithographic printing methods such as offset, roll coater, knife coater, and die coater. It can also be suitably used in various coating methods such as a coater, curtain coater, and spin coater. Moreover, although there is no limitation in particular also about a shaping | molding method, it can use suitably about each shaping | molding systems, such as a pressure molding system, an injection molding system, and an extrusion molding system.

  In the present invention, the cured product obtained by irradiating the energy beam is a product obtained by irradiating the energy beam curable resin composition of the present invention and curing it.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a "part" shows a mass part.

Synthesis example 1
A stirring vessel equipped with a Dean-Stark tube is charged with 20 parts of pentaerythritol, 53.0 parts of acrylic acid, 19.7 parts of dimethylolpropionic acid, 0.265 parts of hydroquinone and 2.65 parts of sulfuric acid, and dehydrated in toluene at 100 ° C. An esterification reaction is performed. After 10 hours from the start of the reaction, the reaction solution was washed with water and 1% NaOH aqueous solution, and then washed with water until the washing water became neutral. The solvent after the water-washed solution was distilled off under reduced pressure using a rotary evaporator to obtain about 83 parts of a polyfunctional monomer (A-1).

The polyfunctional monomer (A-1) thus obtained had a mass average molecular weight of 760 and a viscosity of 2500 mPa · s. The measurement conditions for GPC are as follows.
Model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml per minute, temperature 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene Viscosity was measured with an E-type viscometer manufactured by Toki Sangyo under the conditions of 25 ° C. and 10 to 100 rpm.

  Light for each polyfunctional monomer (A-1), DPHA (Nippon Kayaku dipentaerythritol hexaacrylate), DPHA-40H (monomer having urethane skeleton in which HDI (hexamethylene diisocyanate) is bonded to dipentaerythritol pentaacrylate) A composition in which methyl ethyl ketone was added as a polymerization initiator and a solvent was prepared as shown in Table 1.

Table 1
Composition A Composition B Composition A-1 5 g
DPHA 5g
DPHA-40H 5g
Methyl ethyl ketone 5g 5g 5g
Irg. 184 * 0.25g 0.25g 0.25g

Note * Irg. 184 (Irgacure 184): Ciba Specialty Chemicals (1-hydroxycyclohexyl phenyl ketone)

  The obtained composition was applied to an easy-adhesion-treated polyester film (manufactured by Toyobo Co., Ltd .: A-4300, film thickness 188 μm) using a bar coater (No. 20), and left in a drying oven at 80 ° C. for 1 minute. After that, using a 120 W / cm high-pressure mercury lamp in an air atmosphere, ultraviolet rays were irradiated from a distance of a lamp height of 10 cm at a conveyance speed of 5 m / min to obtain a cured film (3 to 4 μm).

Test Example The obtained cured film was evaluated for the following items, and the results are shown in Table 2.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film was measured using pencil scratching. That is, on a polyester film having a cured film to be measured, a pencil was applied at a 45 degree angle and a 1 kg load was applied from above to scratch about 5 mm to confirm the degree of scratching. Take 5 measurements and count the number of scratches.
Evaluation 5/5: No damage in 5 out of 5 times 0/5: All scratches occurred in 5 times

(curl)
A polyester film having a cured film to be measured was cut into 5 cm × 5 cm, left in an oven at 80 ° C. for 1 hour, and then returned to room temperature. The height of each of the four sides that floated on a horizontal table was measured, and the average value was taken as the measured value (unit: mm). At this time, the curl of the base material itself was 0 mm.

Table 2
Evaluation result test sample Pencil hardness 3H curl
Composition A 4/5 4
Composition B 5/5 8
Composition C 4/5 7

  The composition A using the polyfunctional monomer (A-1) of the present invention has the same level of hardness as the compositions B and C, but has a curl height of about half and less curing shrinkage. Recognize.

  The resin composition of the present invention containing the polyfunctional monomer (A) of the present invention has low curing shrinkage, and the cured product is excellent in hardness. Therefore, the resin composition of the present invention is suitable for hard coat, coating, protective film, ink, insulating layer, adhesive or photoresist ink.

Claims (7)

A polyfunctional monomer (A) obtained by esterifying pentaerythritol, dimethylolpropionic acid and unsaturated monocarboxylic acid in one step. The polyfunctional group according to claim 1, wherein 0.3 to 3.0 molar equivalents of dimethylolpropionic acid and 4.3 to 7 molar equivalents of unsaturated monocarboxylic acid can be esterified in one step to one equivalent of pentaerythritol. Monomer (A). An energy ray-curable resin composition comprising the polyfunctional monomer (A) according to claim 1 or 2. Furthermore, the energy beam curable resin composition of Claim 3 containing a photoinitiator. The energy ray-curable resin composition according to claim 3 or 4, which is a film-forming or insulating material. Hardened | cured material obtained by irradiating an energy ray to the resin composition as described in any one of Claims 2-5. An article having the cured product according to claim 6.