JP2019065150A - (meth) acryl modified aromatic hydrocarbon formaldehyde resin, composition containing the resin, cured product containing the resin and method for producing the resin - Google Patents

Abstract

To provide a (meth) acryl modified aromatic hydrocarbon formaldehyde resin having high reactivity and adhesion, suitable viscosity and hardness, excellent elongation, and excellent optical properties.SOLUTION: A (meth) acryl modified aromatic hydrocarbon formaldehyde resin is obtained by esterification between a polyol modified aromatic hydrocarbon formaldehyde resin and a (meth) acrylic acid or a derivative thereof.SELECTED DRAWING: None

Description

  The present invention relates to a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin and a method for producing the same.

  An aromatic hydrocarbon formaldehyde resin obtained by a method of reacting xylene and formaldehyde under a sulfuric acid catalyst is excellent in compatibility, adhesion, alkali resistance, plasticity, water resistance, transparency and the like, and is epoxy, acrylic, urethane or the like. By adding to or acting on other resins, they are used in various applications such as paints, adhesives and molding materials.

  For example, in Patent Document 1, a removable pressure-sensitive adhesive layer containing a xylene resin and an acrylic resin is provided on one surface of a substrate, and the content of the xylene resin is the total amount with the acrylic resin. There is a description about the removable adhesive tape which is 1 to 70% by weight.

  Patent Document 2 describes a heavy anticorrosive coating composition comprising an epoxy resin, an amine-based curing agent, an aromatic hydrocarbon formaldehyde resin, a pigment, and a solvent.

  In Patent Document 3, urethane prepolymers derived from organic polyisocyanate compounds and polyols, and low molecular weight xylene resins, low molecular weight coumarone resins and low molecular weight styrene resins are selected and have no active hydrogen and are tackifying. There is a description of a reactive hot melt adhesive containing a resin having

  Patent Document 4 describes a one-component moisture-curable urethane-based adhesive using an isocyanate-terminated urethane prepolymer obtained by reacting polyols and an excess of polyisocyanates in the presence of calcium carbonate subjected to surface treatment. is there.

  In Patent Document 5, 15 to 90% by weight of castor oil and 0 to 80% by weight of a polyol having a hydroxyl value of 100 to 600 mg KOH / g and a number average molecular weight of 1100 or less, which is a reaction product of polyhydric alcohol and alkylene oxide, A main agent component comprising 0.1 to 20% by weight of an aromatic diamine, 3 to 40% by weight of a xylene resin, and 1 to 20% by weight of a smoothness aid, and a curing agent component comprising polyisocyanate The urethane resin coating composition is prepared by blending so that the equivalent ratio (NCO / OH) of the isocyanato group to the hydroxyl group of the main agent component is 0.6 to 2.0 / 1.0.

  Furthermore, a phenol-modified aromatic hydrocarbon formaldehyde resin obtained by modifying an aromatic hydrocarbon formaldehyde resin by reaction with phenols improves various properties such as heat resistance, abrasion resistance, and electrical properties, in addition to the applications described above. As an additive, it is also used as a binder for friction materials and as a rubber reinforcing agent.

  For example, in Patent Document 6, an epoxy resin, a curing agent, a curing accelerator, and an inorganic filler are essential components, the curing agent contains a phenol-modified xylene resin, and the curing accelerator is a phosphine compound and a quinone compound. There is a description of a sealing epoxy resin composition obtained by containing an adduct.

  Patent Document 7 discloses a resin composition for a friction material containing a phenol-modified alkyl-substituted aromatic hydrocarbon resin and a reinforcing fiber, which comprises an alkyl-substituted aromatic nucleus and a phenol nucleus in the phenol-modified alkyl-substituted aromatic hydrocarbon resin. There is a description of the resin composition for a friction material, wherein the ratio of is 5:95 to 75:25, and the curing agent of the phenol-modified alkyl-substituted aromatic hydrocarbon resin is hexamethylenetetramine.

  Furthermore, in Patent Document 8, a polyol-type aromatic hydrocarbon obtained by reacting an aromatic hydrocarbon-formaldehyde resin with a polyhydric alcohol as a polyol-type aromatic hydrocarbon formaldehyde resin having a highly reactive alcohol-type hydroxyl group A polyol type aromatic hydrocarbon formaldehyde resin which is a formaldehyde resin and has a formal concentration in the resin of 5% by weight or less and an OH value of 50 to 500 mg KOH / g has been proposed.

  The polyol type aromatic hydrocarbon formaldehyde resin has a highly reactive hydroxyl group in the molecule, and therefore, there is an example of use as a modifier of a polyurethane resin or an acrylic resin.

  For example, Patent Document 9 discloses an acrylic adhesive in which 0.05 to 5 parts by weight of a compound having a tackifying component group and two isocyanate groups as a curing agent is mixed with 100 parts by weight of the solid content of the acrylic main agent. There is a description of the agent.

  Patent Document 10 discloses an isocyanate component comprising a modified product of hexamethylene diisocyanate, and a polyol component comprising an aromatic polyfunctional polyol having a number average molecular weight of 2 to 5 and a liquid polyol having a number average molecular weight within the range of 400 to 800. There is a description about the urethane resin composition for corrosion prevention of the concrete structure for water and sewage which becomes.

Japanese Patent Application Laid-Open No. 2002-146302 JP 2001-152085 A JP-A 5-65471 Japanese Patent Application Laid-Open No. 11-293221 Japanese Patent Application Laid-Open No. 61-223060 JP 2001-114872 A Japanese Patent Application No. 2001-194412 JP-A-4-224815 JP-A-7-126601 Japanese Patent Application Publication No. 2003-268303

  However, in Patent Documents 1 to 5, when an aromatic hydrocarbon formaldehyde resin is added to another resin, there are problems due to low reactivity such as bleed out at the time of heating and a decrease in mechanical strength.

  Further, in Patent Documents 6 and 7, since the phenol-modified aromatic hydrocarbon formaldehyde resin is solid at normal temperature and difficult to handle, the reaction of the phenolic hydroxyl group is limited, so that the application range is limited. .

  Furthermore, in Patent Documents 8 to 10, the polyol type aromatic hydrocarbon formaldehyde resin remains in use as a modifier for other resins that are conventionally used, and makes full use of the characteristics of the highly reactive hydroxyl group. Absent.

  In addition, in the fields of ink, paint, and optical materials, materials that can be applied to highly productive processes that are cured instantaneously by UV (ultraviolet) or EUV (extreme ultraviolet) are required.

  This invention is made in view of the said subject, has high reactivity and adhesiveness, has suitable viscosity and hardness, has favorable elongation, and is (meth) acrylic-modified which is excellent in an optical characteristic. An aromatic hydrocarbon formaldehyde resin, a composition containing the resin, a cured product obtained by curing the composition, a cured product obtained by curing the resin, and a manufacturing method.

The present inventors can use a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin obtained by subjecting a polyol-modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid or a derivative thereof to an esterification reaction. It has been found that the above problems can be solved, and the present invention has been completed.
In addition, the present inventors react polyol-modified aromatic hydrocarbon formaldehyde resin with (meth) acrylic acid or a derivative thereof to obtain polyol-modified aromatic hydrocarbon formaldehyde resin having high reactivity, and this resin is It was found that UV, EUV and the like cure instantaneously, and the present invention was completed.

  That is, the present invention includes the following contents.

  [1] A (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin obtained by subjecting a polyol-modified aromatic hydrocarbon-formaldehyde resin and (meth) acrylic acid or a derivative thereof to an esterification reaction.

  [2] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to [1], having a weight average molecular weight (Mw) of 300 to 10,000.

  [3] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to [1] or [2], which has an ester value of 20 to 850 mg KOH / g.

  [4] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of [1] to [3], which has a viscosity of 1,000 Pa · s or less at 25 ° C.

  [5] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of [1] to [4], wherein the polyol-modified aromatic hydrocarbon formaldehyde resin contains a polyol-modified xylene resin.

  [6] The (meth) according to any one of [1] to [6], wherein the polyol-modified aromatic hydrocarbon formaldehyde resin is obtained by reacting an aromatic hydrocarbon formaldehyde resin with a polyol under an acidic catalyst. Acrylic modified aromatic hydrocarbon formaldehyde resin.

  [7] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of [1] to [6], wherein the hydroxyl value of the polyol-modified aromatic hydrocarbon formaldehyde resin is 20 to 850 mg KOH / g.

  [8] The (meth) acrylic modified aromatic carbonization according to any one of [1] to [7], wherein the weight average molecular weight (Mw) of the polyol modified aromatic hydrocarbon formaldehyde resin is 250 to 10,000. Hydrogen formaldehyde resin.

  [9] A composition comprising the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of [1] to [8].

  [10] A cured product obtained by curing the composition according to [9].

  [11] A cured product obtained by curing the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of [1] to [8].

  [12] A method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, comprising the step of esterifying a polyol-modified aromatic hydrocarbon-formaldehyde resin and (meth) acrylic acid or a derivative thereof.

  [13] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to [12], including the step of dehydration esterification of the polyol-modified aromatic hydrocarbon formaldehyde resin and the (meth) acrylic acid under an acid catalyst Manufacturing method.

  [14] The (meth) acrylic-modified aromatic hydrocarbon formaldehyde according to [12], comprising the step of esterifying the polyol-modified aromatic hydrocarbon formaldehyde resin with the (meth) acrylic acid derivative under an ester exchange catalyst Manufacturing method of resin.

  [15] The method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to [12] or [14], wherein the (meth) acrylic acid derivative contains a (meth) acrylic acid alkyl ester.

  According to the present invention, (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin having high reactivity and adhesion, suitable viscosity and hardness, good elongation, and excellent optical properties You can get the way.

  Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described. Note that the following present embodiment is an example for describing the present invention, and the present invention is not limited to the present embodiment.

  In the present specification, "(meth) acryloyl group" means both "acryloyl group" and "methacryloyl group" corresponding thereto, and "(meth) acrylate" means "acrylate" and corresponding methacrylate The term "(meth) acrylic acid" means both "acrylic acid" and the corresponding "methacrylic acid".

  Further, in the present embodiment, “resin solid content” or “resin solid content in resin composition” means components in the resin composition excluding the solvent and the filler, unless otherwise specified. The solid content of 100 parts by weight means that the total of components excluding the solvent and the filler in the resin composition is 100 parts by weight.

[(Meth) Acryl-Modified Aromatic Hydrocarbon Formaldehyde Resin]
The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of this embodiment is a (meth) acrylate derivative of a polyol-type aromatic hydrocarbon formaldehyde resin.

  The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of this embodiment is obtained by subjecting a polyol-modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid or a derivative thereof to an esterification reaction.

  The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment has a highly reactive functional group and is a mixture of various structures, so it is excellent in adhesion and adhesiveness, and has a suitable viscosity and phase. Soluble, good elongation, excellent dispersibility, excellent toughness and flexibility, excellent heat resistance and water resistance, excellent chemical resistance, high transparency, color change It is also difficult to use and is excellent in optical characteristics such as being amorphous.

  Moreover, since the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of this embodiment has excellent reactivity, a cured product can be easily obtained by UV irradiation. Therefore, when cured alone, a film excellent in flexibility, adhesion and transparency can be formed, and when it is added to other resins and cured, bleeding out during heating, decrease in mechanical strength, etc. Not cause.

  The weight average molecular weight (Mw) of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 300 to 10,000 in terms of polystyrene. More preferably, it is 300-4,000, More preferably, it is 300-2,000 from a viewpoint of handleability. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

  The ester value of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of this embodiment is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 20 to 850 mg KOH / g, more preferably 50 to 500 mg KOH / g And more preferably 100 to 200 mg KOH / g from the viewpoint of UV curing.

  The viscosity at 25 ° C. of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 1,000 Pa · s or less, more preferably 0. The pressure is 001 to 1,000 Pa · s, more preferably 0.05 to 500 Pa · s, and still more preferably 0.1 to 100 Pa · s.

  The viscosity at 75 ° C. of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 50 Pa · s or less, more preferably 20 Pa · s or less More preferably, it is 10 Pa · s or less.

[Method for producing (meth) acrylic modified aromatic hydrocarbon formaldehyde resin]
The method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment includes the step of esterifying a polyol-modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid or a derivative thereof. The esterification is not particularly limited as long as it is a known esterification, and examples thereof include a dehydration esterification method and a transesterification method.

[Production method including dehydration esterification method]
The method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment preferably includes a step of dehydration esterification of a polyol-modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid under an acidic catalyst . In the step, dehydration esterification may be used in the presence of a polymerization inhibitor comprising a copper compound and a phenolic compound, together with an acidic catalyst.

The acidic catalyst is not particularly limited, and any known acidic catalyst can be used. For example, sulfuric acid, hydrochloric acid, phosphoric acid, fluoroboric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, cation exchange resin and the like can be mentioned. Among these, sulfuric acid and p-toluenesulfonic acid are preferable from the viewpoint of easy availability, low cost, and excellent reactivity. These acidic catalysts may be used alone or in combination of two or more.
As a ratio of an acidic catalyst, 0.01-10 mol% is normally preferable with respect to charge (meth) acrylic acid.

The polymerization inhibitor is not particularly limited, but preferably comprises a copper compound and a phenol compound. A polymerization inhibitor can be used individually by 1 type or in mixture of 2 or more types suitably.
The copper compound may be an anhydride or a hydrate, and cupric halides such as cupric chloride and cupric bromide; halogens such as cuprous chloride and cuprous bromide Cuprous bromide; copper sulfate; and copper dialkyldithiocarbamates such as copper dimethyldithiocarbamate and copper dibutyldithiocarbamate. Among these, cupric chloride and copper sulfate are preferred because they have a strong polymerization inhibiting action and are inexpensive.

  As a phenolic compound, hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethyl Examples include phenol, 2,6-di-tert-butyl-4-methyl-phenol, 2,4,6-tri-tert-butylphenol and the like. Among these, hydroquinone and hydroquinone monomethyl ether are preferable because they are inexpensive and can be easily removed by neutralization washing after dehydration esterification.

  In general, the addition ratio of the polymerization inhibitor is preferably 5 to 20,000 ppm by weight, more preferably 25 to 3,000 ppm by weight, based on the reaction solution, for both of the copper compound and the phenol compound. If the addition ratio is less than 5 ppm by weight, the effect of inhibiting polymerization may be insufficient. If it exceeds 20,000 ppm by weight, the effect will not be improved even if it is added more than this, which is uneconomical, and there is a possibility that the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin obtained may be colored.

  The esterification reaction of the polyol modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid may be performed according to a conventional method. The method etc. of heating and stirring and esterifying polyol modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid in presence of an acidic catalyst and a polymerization inhibitor etc. are mentioned.

  The reaction ratio of the polyol-modified aromatic hydrocarbon formaldehyde resin and (meth) acrylic acid is not particularly limited, and usually, the ratio of (meth) acrylic acid to 1 mol of all hydroxyl groups in the polyol-modified aromatic hydrocarbon formaldehyde resin Adjust the The proportion of (meth) acrylic acid is preferably 0.5 to 3 moles with respect to 1 mole of all hydroxyl groups in the polyol-modified aromatic hydrocarbon formaldehyde resin.

  The end point of the esterification reaction may be determined by the amount of by-product water and the like.

  The esterification reaction can be carried out without solvent or with a solvent. Since an esterification reaction forms water with the progress of the reaction, it is preferable to use a solvent capable of removing water azeotropically in view of enhancing the reaction rate.

The solvent is not particularly limited, but, for example, aromatic hydrocarbons such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-hexane, cyclohexane and n-heptane; organic compounds such as trichloroethane, tetrachlorethylene and methyl chloroform Chlorinated compounds; ketones such as methyl isobutyl ketone and the like can be mentioned. These solvents may be used alone or in combination of two or more.
The amount of the solvent used is not particularly limited, but is preferably 0.1 to 10 times by weight, more preferably 2 to 5 times by weight, relative to the reaction material.

  The reaction temperature is not particularly limited, but is preferably 65 to 140 ° C., more preferably 75 to 120 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. If the temperature is less than 65 ° C., the reaction rate may be too slow and the yield may be decreased. If the temperature exceeds 140 ° C., the thermal polymerization of the (meth) acrylic acid or (meth) acrylic modified aromatic hydrocarbon formaldehyde resin may occur is there.

  The reaction is preferably carried out under normal pressure or under slightly reduced pressure.

  In order to prevent thermal polymerization of the (meth) acrylic acid or the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, it is preferable to react in the presence of oxygen during the esterification reaction. Specifically, there is a method of carrying out an esterification reaction while blowing an inert gas containing oxygen into the reaction liquid. The inert gas may, for example, be nitrogen or helium, preferably nitrogen from the viewpoint of low cost.

  In the reaction, in addition to the above-mentioned polymerization inhibitors, other polymerization inhibitors may be used in combination as needed. Specifically, for example, quinone type polymerization inhibitors such as p-benzoquinone and naphthoquinone, thiophenol type polymerization inhibitors such as 3-hydroxythiophenol, naphthol type polymerization inhibitors such as α-nitroso-β-naphthol, alkyl And amine polymerization inhibitors such as diphenylamine, N, N'-diphenyl-p-phenenamine and phenothiazine. These other polymerization inhibitors may be used alone or in combination of two or more.

  The reactor used for the reaction is not particularly limited, and examples thereof include a reactor equipped with a stirrer, a thermometer, an air blowing pipe, and a water separator.

The reaction product obtained by the esterification reaction may be purified according to a conventional method.
Specifically, the reaction solution may be neutralized and washed with water, the aqueous layer may be separated, the reaction solvent may be distilled off under reduced pressure, and the reaction may be filtered if necessary.
The neutralization step is carried out for the purpose of removing unreacted (meth) acrylic acid and the acidic catalyst in the reaction liquid. The neutralization process includes a method of adding an alkaline aqueous solution to the reaction solution and stirring.

[Production method including transesterification method]
The method for producing the (meth) acrylic modified aromatic hydrocarbon formaldehyde resin of the present embodiment includes the step of esterifying the polyol modified aromatic hydrocarbon formaldehyde resin and the (meth) acrylic acid derivative under an ester exchange catalyst preferable.

  Transesterification is known to be reversible, and in order to complete the reaction, it is preferable to remove one of the reaction products out of the system. Selecting a carboxylic acid ester in which the alcohol residue portion of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin is a lower alkyl group, such as a methyl group, an ethyl group, a propyl group or a butyl group, a low boiling point monohydroxy group containing alcohol (For example, methanol, ethanol, butanol) are produced in the transesterification step, and they are preferable because they are easily removed out of the reaction system.

  The transesterification catalyst is not particularly limited as long as it is a substance that promotes transesterification, and acidic catalysts, Lewis acid catalysts, basic catalysts, and metal catalysts are suitably used. These transesterification catalysts can be used individually by 1 type or in mixture of 2 or more types. Among these, metal catalysts are particularly preferably used.

  Examples of the acidic catalyst include sulfuric acid and p-toluenesulfonic acid.

  Examples of the Lewis acid catalyst include titanate esters, zinc acetate, zinc acetylacetone, dibutyltin oxide and the like.

  As the basic catalyst, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium methoxide and the like can be mentioned.

  The metal catalyst is not particularly limited, but is preferably a catalyst containing one metal compound containing a metal of Group II and / or Group IV of the periodic table and a phosphine compound.

  The metals belonging to group II of the periodic table are beryllium, magnesium, calcium, zinc, strontium, cadmium, barium, mercury and radium. Among these, magnesium, calcium, zinc, strontium, cadmium, barium and mercury are preferable, magnesium and zinc are more preferable, and further preferable metals are zinc.

  The metals belonging to group IV of the periodic table are carbon, silicon, germanium, titanium, tin, zirconium, lead, hafnium. Among these, tin, zirconium and lead are preferable, tin and zirconium are more preferable, and a further preferable metal is tin.

The metal compound may be, for example, a metal itself such as metal tin, metal lead or metal zinc, or an organic or inorganic compound of a metal, and the form thereof may be any form such as powder. One form of metal compound includes salts of metals, such as organic salts and inorganic salts. They are generally represented by MX _2. Here, M is a divalent metal selected from Group II or Group IV of the periodic table, X is -OCOR or a halogen atom, and R is an alkyl group containing 1 to 20 carbon atoms .

  Preferred metal salts are carboxylates of metals selected from magnesium, calcium, zinc, barium, mercury and lead, and examples thereof include acetic acid, oxalic acid, propionic acid, butyric acid, octylic acid, maleic acid, boric acid and citric acid. It is a salt of acid, caproic acid, stearic acid. Further, halides such as chlorides and bromides of these metals are also preferable. The most preferable metal salt is a carboxylate of zinc, magnesium or lead, and examples thereof include zinc acetate, magnesium acetate, lead acetate, lead acetoacetate and the like.

  The metal compounds may be organometallic compounds represented by the following general formulas (1) to (4).

In the above general formula, M ¹ is a metal of Group IV of the periodic table, R ¹ is an alkyl group having 1 to 20 carbon atoms, and Y is -R ² , -OCOR ² , -CH (COCH ₃ ) ₂ , a hydrogen atom or a halogen atom, and R ² represents an alkyl group having 1 to 20 carbon atoms.

  The metal compound represented by the above general formula is not particularly limited, but dialkyl metal oxides, dialkyl metal dihalides, dialkyl metal dicarboxylates and metal acetylacetonate are preferable. Among them, dialkyltin oxides, dialkyltin dihalides, dialkyltin dicarboxylates, zirconium acetylacetonate and the like are preferable, and dimethyltin dichloride, diethyltin dichloride, dibutyltin dichloride, zirconium acetylacetonate and the like More preferable.

  The phosphine compound is not particularly limited, but is represented by the following general formula (5).

  In general formula (5), R1, R2 and R3 each independently represent an aliphatic group, an alicyclic group or an aromatic group, and the aliphatic group or the alicyclic group has a saturated or unsaturated carbon number The aromatic group may be a monocyclic, polycyclic or fused ring, and may be substituted or unsubstituted.

  Specifically, trialkyl phosphines such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, tripentyl phosphine, trioctyl phosphine, triphenyl phosphine, tribenzyl phosphine, tritolyl phosphine, triflyl phosphine, diphenyl- 2-pyridylphosphine, 4-dimethylaminophenyldiphenylphosphine, 1,2-bisdiphenylphosphinoethane, 1,2-bisdiphenylphosphinopropane, 1,2-bisdiphenylphosphinoferrocene, 2,2′-bisdiphenyl Phosphino 1,1-binaphthyl, tridimethoxyphenyl phosphine, tritolyl phosphine and the like can be mentioned.

  Among them, trialkyl phosphines such as trimethyl phosphine, triethyl phosphine, tripropyl phosphine and tributyl phosphine and triphenyl phosphine are preferably used.

  In the production method including the transesterification method according to the present embodiment, it is preferable to inhibit the polymerization of unsaturated bond occurring during the reaction by the polymerization inhibitor, and as these polymerization inhibitors, polymerization inhibition of known and commonly used polymer synthesis is The agent can be used without particular limitation.

  Examples of the polymerization inhibitor include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butyl catechol, t-butyl phenol, dimethyl-t-butyl phenol, t-butyl cresol, phenothiazine and the like. You may use these 1 type or in combination of 2 or more types.

  The amount of the polymerization inhibitor depends on the amounts of raw materials and products, and is not particularly limited, but usually 5 to 10,000 ppm by weight, preferably 20 to 10,000 ppm by weight based on the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin. ~ 7,000 ppm by weight.

  The molar ratio of the (meth) acrylic acid derivative to the polyol-modified aromatic hydrocarbon formaldehyde resin used in the transesterification reaction can be varied within a wide range, but the ratio is usually 1 or more, preferably (meth) acrylic acid The molar ratio of derivative to polyol modified aromatic hydrocarbon formaldehyde resin to hydroxyl group is between 1.1: 1 to 10: 1.

  The amount of the transesterification catalyst is preferably 0.01 to 10.0 mol%, more preferably 0.05 to 7.0 mol%, with respect to the hydroxyl group of the polyol-modified aromatic hydrocarbon formaldehyde resin. The molar ratio of tert-phosphine compound to metal compound can vary from 1:10 to 10: 1, but is preferably in the range of 1: 5 to 5: 1.

  When two components of a metal compound and a phosphine compound are contained as the metal catalyst, these may be simultaneously added to the reaction system or may be separately added to the reaction system. When the two components are added simultaneously, they may be added as a single dose at the start of the reaction, or may be divided into two or more portions and administered to the reaction system. Also, since the properties of the organic metal catalyst to be used are slightly different from each other, the number of hydroxyl groups contained in the polyol-modified aromatic hydrocarbon formaldehyde resin and the number of ester groups of the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin It is preferable to select and use a metal catalyst appropriately.

  Alternatively, the two components may be added separately. For example, when only the phosphine compound is added to the reaction system at the start of the reaction and allowed to react for a while (for example, after 2 hours), the metal compound is added to the reaction system The reaction rate is preferred because the reaction rate is faster than adding the two components simultaneously at the start of the reaction, and the reaction time is shortened.

  The transesterification reaction can be carried out either in the absence of a solvent or in the presence of a suitable solvent which does not affect the transesterification reactants. Usually, no solvent is required except in the following cases.

  (1) In order to complete the transesterification reaction, it is necessary to remove one of the reaction products (usually, the alcohol formed) out of the system. The alcohol can be removed more efficiently by adding a co-solvent with the aliphatic or cycloaliphatic hydrocarbon solvent which forms a lower azeotropic point with the alcohol to the reaction mixture.

  The solvent may be added to the reaction mixture in an amount of about 5 to 50% by weight, preferably 10 to 30% by weight of the starting material, which does not affect the transesterification reaction. Suitable solvents are aliphatic, cycloaliphatic hydrocarbons having 4 to 10 carbon atoms, more preferably 5 to 7 carbon atoms, or mixtures thereof. These hydrocarbon solvents are recovered by azeotropic distillation and can be regenerated by extracting the alcohol with water.

  (2) Inert and high boiling solvents may be added to increase the reaction temperature. Solvents of this type are aliphatic or cycloaliphatic hydrocarbons, and several aromatic hydrocarbons, which can be recovered by distillation after the reaction is completed.

  (3) When it is difficult to dissolve in (meth) acrylic acid ester, a suitable solvent for dissolving the polyol-modified aromatic hydrocarbon formaldehyde resin is added to the reaction mixture to convert the heterogeneous reaction into a homogeneous reaction, and the reaction rate You can speed up Examples of such solvents include highly polar aprotic solvents containing a nitrogen atom or a sulfur atom, and examples thereof include formamide, N, N-dimethylformamide, N, N-dimethylacetamide, sulfolane and dimethyl sulfoxide. , Dimethyl sulfone and the like.

  The reaction is usually carried out at atmospheric pressure, and the reaction temperature can be appropriately selected depending on the raw material and the reaction solvent. Generally, the higher the reaction temperature, the faster the reaction rate. The reaction temperature is usually 20 to 160 ° C, preferably 30 to 150 ° C, and more preferably 60 to 130 ° C.

  If the reaction temperature exceeds 160 ° C., there is a risk that polymerization may occur, and by-products may be easily formed. On the other hand, if the reaction temperature is less than 20 ° C., the reaction rate may be slow and not practical. The reaction can be carried out under reduced pressure to remove the alcohol formed. When the reaction temperature is defined by the boiling point of the alcohol to be removed, the reaction temperature is usually 60 to 120 ° C.

  In the method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, a polyol-modified aromatic hydrocarbon formaldehyde resin and a (meth) acrylic acid derivative in an appropriate ratio, such as a thermometer, a stirrer, a fractionating tube, and dry air Charge into a reactor equipped with an introductory tube. Next, an appropriate amount of catalyst, polymerization inhibitor and, if necessary, solvent are added to the reaction mixture. The method of adding the catalyst also differs depending on the type of catalyst used, for example, it is better to add only the phosphine compound to the reaction mixture first than to the case where the phosphine compound and the metal compound are added simultaneously to the reaction mixture at the start of the reaction, In some cases, the reaction rate is fast and the reaction time can be shortened.

  While stirring the reaction mixture, it is heated to an appropriate temperature range, usually 20 to 160 ° C., preferably 30 to 150 ° C., more preferably 60 to 130 ° C., usually to the reflux temperature of the reaction system. In order to complete the reaction while stirring the reaction mixture, the alcohol produced by the transesterification reaction during the reaction is often separated off as azeotrope with the excess (meth) acrylate or reaction solvent, by means of a fractionating tube Remove. At the same time, the same amount of (meth) acrylic acid ester or reaction solvent is optionally added to the reaction mixture to keep the amount of contents of the reactor constant.

  The end point of the esterification reaction may be determined by quantitative analysis of the amount of removed alcohol by GC (gas chromatography) or the like. After completion of the reaction, excess (meth) acrylic acid ester or reaction solvent is distilled off from the reactor, and a small amount of inert solvent such as toluene or heptane is added from the reactor as needed to take out the crude ester. The reaction product is removed from the reaction vessel while leaving a small amount of (meth) acrylic acid ester.

  The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin is obtained by filtering the reaction product or washing with water or washing with an alkaline solution to remove unnecessary substances such as catalyst metals and distilling off the solvent and the like. it can.

[Polyol Modified Aromatic Hydrocarbon Formaldehyde Resin]
The polyol-modified aromatic hydrocarbon formaldehyde resin preferably comprises a polyol-modified xylene resin.

  The polyol-modified xylene resin is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably contained in 50% by weight or more, and more preferably 80% by weight or more in 100% by weight of the polyol-modified aromatic hydrocarbon formaldehyde resin . The upper limit is not particularly limited, but is 100% by weight.

  The polyol-modified xylene resin is a resin obtained by reacting a xylene resin and a polyhydric alcohol, and is a resin having a highly reactive alcoholic hydroxyl group. It is used for reforming various resins such as acrylic resin, urethane resin, epoxy resin and the like.

  The hydroxyl value of the polyol-modified aromatic hydrocarbon formaldehyde resin is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 20 to 850 mg KOH / g, more preferably 50 to 600 mg KOH / g, and still more preferably And 100 to 400 mg KOH / g from the viewpoint of UV curability after acrylic modification.

  The weight average molecular weight (Mw) of the polyol-modified aromatic hydrocarbon formaldehyde resin is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably 250 to 10,000, and more preferably 250 to 10,000 in terms of polystyrene. And more preferably from 250 to 2,000 from the viewpoint of UV curing after acrylic modification. The weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

  The polyol-modified aromatic hydrocarbon formaldehyde resin is obtained by reacting an aromatic hydrocarbon formaldehyde resin with polyols under an acidic catalyst.

  The polyol modified aromatic hydrocarbon formaldehyde resin can be synthesized, for example, based on the method described in JP-A-4-224815. Moreover, for example, commercially available products such as K100E, K140, and K140E manufactured by Hudoh Co., Ltd. can be used.

[(Meth) acrylic acid or its derivative]
Examples of (meth) acrylic acid or derivatives thereof include (meth) acrylic acid, salts of such metal salts and ammonium salts, and (meth) acrylic acid esters. These (meth) acrylic acids or their derivatives can be used alone or in combination of two or more.
As the (meth) acrylic acid ester, an ester of (meth) acrylic acid and an alcohol having 1 to 18 carbon atoms is preferable, and a (meth) acrylic acid alkyl ester is more preferable. Also, these (meth) acrylic acids or their derivatives may have a functional group. As a functional group, a hydroxyl group, a tetrahydrofurfuryl group, an epoxy group etc. are mentioned.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, butyl (meth) acrylate, An isobutyl (meth) acrylate etc. are mentioned. Among these, methyl (meth) acrylate and ethyl (meth) acrylate are preferable from the viewpoint of boiling point (reaction temperature).

[Composition Comprising (Meth) Acryl-Modified Aromatic Hydrocarbon Formaldehyde Resin]
The composition of the present embodiment comprises a (meth) acrylic modified aromatic hydrocarbon formaldehyde resin.

  In the composition of the present embodiment, a (meth) acrylic resin other than the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, an epoxy resin, a cyanate ester compound, and a phenol resin, as long as the characteristics of the present embodiment are not impaired. Resins such as oxetane resins and benzoxazine compounds, various polymers such as oligomers, elastomers, monomers having polymerizable functional groups such as compounds having an ethylenically unsaturated group, maleimide compounds, fillers, flame retardants, A silane coupling agent, a wetting and dispersing agent, a photopolymerization initiator, a photocuring initiator, a thermal curing accelerator, various additives, and the like can be included. The components contained in the composition of the present embodiment are not particularly limited as long as they are generally used.

  In addition, as various additives, UV absorbers, antioxidants, optical brighteners, photosensitizers, optical brighteners, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, surface conditioning Agents, brighteners, polymerization inhibitors and the like.

It is also possible to use the said component individually by 1 type or in mixture of 2 or more types suitably.
Moreover, the compounding quantity of each component can also be variously prepared according to a use.

[Method of producing composition]
The composition of the present embodiment is prepared by appropriately mixing the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin and each of the above-described components as necessary.

  The method for producing the composition is not particularly limited, and examples thereof include a method in which the respective components are sequentially mixed in a solvent and sufficiently stirred.

  At the time of production of the composition, known treatments (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing the respective components can be performed, if necessary. The stirring, mixing, and kneading processes are, for example, a stirring device for the purpose of dispersion such as ultrasonic homogenizer, a three-roll, a device for the mixing such as ball mill, bead mill and sand mill, or a revolving or rotation type mixing device It can carry out suitably using well-known apparatuses, such as.

  At the time of preparation of the composition of the present embodiment, an organic solvent can be used as needed. The type of the organic solvent is not particularly limited as long as the resin in the composition can be dissolved.

  The organic solvent is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof It can be mentioned. These organic solvents may be used alone or in combination of two or more.

[Cured product]
The cured product of the present embodiment is obtained by curing a (meth) acrylic modified aromatic hydrocarbon formaldehyde resin or composition.

  The cured product can be obtained by various known methods. As a curing method, for example, irradiation with UV or EUV, heating, etc. may be mentioned, and it is also possible to use these in combination.

  The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment has high reactivity, and thus is suitable for a highly productive process of instantaneously curing by UV or EUV. Moreover, since it has high reactivity, high quality hardened | cured material can be supplied stably. The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment is also excellent in optical properties, and has high transparency even in a cured product. Therefore, the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin and the cured product of the present embodiment can be suitably used in the fields of ink, paint, and optical material.

Case of ultraviolet irradiation can adjust its dose optionally, the irradiation can be carried out, for example 0.05J / cm ² ~10J / cm ² approximately dose.

  The heating conditions may be appropriately selected according to the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, each component in the composition containing the resin, the content of the resin and each component, etc. Is selected in the range of 20 minutes to 180 minutes at 150 ° C. to 220 ° C., more preferably in the range of 30 minutes to 150 minutes at 160 ° C. to 200 ° C.

[Use]
The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin, the composition and the cured product of this embodiment can be used for various applications.

  For example, applications such as adhesives and adhesives, home appliances such as touch panels, various lens materials, optical materials such as dental materials and medical materials applications, applications of automobiles and building materials such as paints, coatings and primers, and artificial such as shoes, bags and school bags Leather and synthetic leather applications, knit products, synthetic fiber applications such as spandex, polymerization raw materials, molding materials, gas separation membranes, membranes for fuel cells, optical waveguides, holograms, etc. may be mentioned.

  In particular, various UV curable paints and coatings such as automotive, mobile terminal and light electrical products, optical disks, optical fibers, cosmetic containers, building materials and floors, self-healing paints and coatings, UV curable ink jet inks , UV curable resin for nanoimprint, UV curable resin for 3D printer, UV ink such as photosensitive conductive paste, UV curable adhesive, OCA for touch panel, OCR for touch panel, UV adhesive such as seal material for organic EL, Materials for buffer coat films, lenses (pickup lenses, microlenses, spectacle lenses), polarizing films (for liquid crystal displays etc.), antireflection films (for antireflection for display devices etc.), films for touch panels, films for flexible substrates, displays Film [PDP (plasma Displays) such as LCD (Liquid Crystal Display), VFD (Vacuum Fluorescent Display), SED (Surface Conduction Electron Emission Device Display), FED (Field Emission Display), NED (Nano Emissive Display), Braun Tube, Electronic Paper, etc. It can utilize suitably for optical materials, such as films (a filter, a protective film, etc.) etc. (especially thin display).

[Raw materials and modifiers such as acrylic resin, vinyl ester resin, alkyd resin, epoxy resin, and unsaturated polyester resin]
Raw materials such as urethane resin, acrylic resin, vinyl ester resin, alkyd resin, epoxy resin, and unsaturated polyester resin, additives to the resin, and modifiers of the (meth) acrylic modified aromatic hydrocarbon formaldehyde resin of the embodiment When used for example, the water resistance, chemical resistance, and heat resistance of these resins can be improved.

  The urethane resin refers to a polymer compound having a urethane bond, and is, for example, a resin obtained by polymerization addition of an aliphatic diamine or glycol and a diisocyanate.

  An acrylic resin is obtained by copolymerizing acrylic acid or methacrylic acid, and several (meth) acrylic monomers of these derivatives. Examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) acrylate.

  The vinyl ester resin is obtained, for example, by adding a reaction product obtained by adding an epoxy group and approximately equimolar α, β-unsaturated monobasic acid to a polyepoxide in the presence of an addition catalyst with a polymerizable monomer such as styrene. It is a resin obtained by mixing and adding a polymerization inhibitor etc. as needed.

  The alkyd resin is a resin obtained by condensing a polyhydric alcohol and a polybasic acid. Examples of polyhydric alcohols include glycerin, pentaerythritol, neopentyl glycol, ethylene glycol, diethylene glycol and the like. Examples of polybasic acids include phthalic anhydride and maleic anhydride.

  The epoxy resin is a resin having an epoxy group which is cured by an amine, an acid anhydride or the like, and for example, a resin obtained by the reaction of an epoxy compound and a bisphenol or polyhydric alcohol, an unsaturated group is epoxidized by a peracid The obtained resin etc. are mentioned. Specifically, as an epoxy resin having an amine as a precursor, tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, and various isomers of triglycidylaminocresol are mentioned. Be As an epoxy resin which makes phenols a precursor, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy Resin, resorcinol type epoxy resin is mentioned. As an epoxy resin which uses a compound which has a carbon and a carbon double bond as a precursor, an alicyclic epoxy resin is mentioned.

  The unsaturated polyester resin is obtained, for example, by mixing an unsaturated polyester obtained by reacting an acid such as unsaturated dibasic acid and an alcohol with a polymerizable monomer such as styrene, and adding a polymerization inhibitor and the like as necessary. Resin obtained by As the acid, for example, unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and anhydrides of these acids can be mentioned. As a part of these unsaturated dibasic acids, phthalic acid, isophthalic acid, terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid, etc., or anhydrides of these acids may be used. Examples of the alcohol include ethylene glycol, propylene glycol, 1,3-methylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, hexylene glycol and the like. As part of these, monohydric alcohols such as cyclohexyl alcohol and benzyl alcohol, or polyhydric alcohols such as glycerin and trimethylolpropane may be used.

  EXAMPLES The present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited by these Examples.

[Measurement and evaluation method]
(1) Weight average molecular weight (Mw)
It measured using a Showa Denko GPC apparatus. In addition, polystyrene was used for preparation of a calibration curve.
Device: Shodex (registered trademark) GPC-101 (manufactured by Showa Denko KK)
Column: Shodex (registered trademark) KF-801 × 2, KF-802.5, KF-803L
Eluent: tetrahydrofuran Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Detector: RI (differential refraction detector)

(2) Ester value According to JIS K 0070, a saponification value and an acid value were measured by the neutralization titration method, and were calculated by the following formula.
Ester value = Saponification value-Acid value

(3) Viscosity (Pa · s, CP, 25 ° C or 75 ° C)
It measured according to JISK6833 using a rotational viscometer.
Note that K100E manufactured by Fudoh Co., Ltd., which is a xylene resin modified with a polyol, is measured at 25 ° C., and K140 manufactured by Fudoh Co., Ltd. and K140E manufactured by Fudoh Co., Ltd., which is a xylene resin modified with a polyol, is measured at 75 ° C.

(4) Hydroxyl value (OH number, mg KOH / g)
It measured by the acetic anhydride-pyridine method (JIS K 0070).

(5) Curability The obtained compounded composition was coated on a polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd., PET film) using a bar coater, and 250 mJ / cm ² using an ultraviolet irradiation apparatus (high pressure mercury lamp). Under the conditions of (1), UV irradiation was repeated until no tack was present, to obtain a cured coating. In the case where the required number of times of irradiation at this time was 2 or less, it was evaluated as 、;

(6) Rubbing test The obtained cured coating film was rubbed with a cotton swab impregnated with acetone. When the surface was not dissolved, it was evaluated as 〇, and when it was dissolved, it was evaluated as x.

(7) Curl 50 mm × 100 mm PET # 50 for bar coater No. The film was coated using No. 60, and the curl when the cured coating was obtained was measured. When the curl was within 10 mm, it was evaluated as 、, within 25 mm and when it did not curl inward, it was evaluated as Δ, and when it was curled inward, it was evaluated as x.

(8) Yellow Index (YI)
It measured using the Nippon Denshoku Co., Ltd. product made from Nippon Denshoku Co., Ltd. color / turbidity simultaneous measurement device (COH 400) using the obtained cured coating film. In addition, separately, measurement was implemented by PET film alone and it was set as the blank.

(9) Haze
It measured using the Nippon Denshoku Co., Ltd. product made from Nippon Denshoku Co., Ltd. color / turbidity simultaneous measurement device (COH 400) using the obtained cured coating film. Separately, the measurement was carried out with a PET film alone to make a blank.

(10) Total light transmittance (TT,%)
Using the obtained cured coating film, it measured using Nippon Denshoku Co., Ltd. color and turbidity simultaneous measuring instrument COH400. Separately, the measurement was carried out with a PET film alone to make a blank.

(11) Growth (%)
About the obtained cured coating film, it measured using Toyo Seiki Co., Ltd. product STROGRAPH E2L05 / RCT-500N-EA. The sample was cut into a width of 1 cm, and the distance between the chucks was 5 cm. The elongation was calculated from the magnitude of the displacement when the cured coating broke.

(12) Chemical resistance The obtained cured coating film was coated with Neutrogena (sunscreen), allowed to stand in an environment of 60 ° C. for 1 day, washed with water, and then it was confirmed whether or not a mark remained. In the case where there was no mark, it was evaluated as 〇, in the case where the mark remained, it was evaluated as Δ, and in the case where the coating film was dissolved, it was evaluated as ×.

(13) Adhesiveness With respect to the obtained cured coating film, peeling of the coating film was tried by bending or scratching the film.
When it peeled off, it was set as x, and when it did not peel, it was set as evaluation of (circle).

  Physical properties of KDO, K140E, and K100E manufactured by Fudo Co., Ltd., which are xylene resins modified with a polyol, are shown in Table 1.

Example 1
78.7 parts of KDO manufactured by Hudoh Co., Ltd., 150.7 parts of methyl acrylate, 0.2 parts of polymerization inhibitor A (hydroquinone manufactured by Wako Pure Chemical Industries, Ltd.) and B (p-methoxyphenol manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 parts were charged to a 500 ml reaction flask equipped with a thermometer, a fractionating tube and a glass tube for flowing dry air.

  Next, 1.65 parts of dimethyltin dichloride and 0.40 parts of sodium methoxide were added to the reaction mixture under stirring. The reaction mixture was heated under reflux at 85 ° C. under normal pressure while stirring, and the azeotropic mixture of methanol and methyl acrylate was removed from the upper part of the distillation tube from the reaction system. At the same time, the same amount of methyl acrylate was added to the reaction system to maintain the amount of contents of the reactor. The reaction time was 6 hours. After completion of the reaction, excess methyl acrylate was removed under reduced pressure with heating at 80.degree. The reaction product is diluted with 150 parts of toluene and then washed with a 20% aqueous solution of sodium hydroxide to remove tin catalyst and polymerization inhibitor, and finally, toluene is removed by distillation under reduced pressure to obtain acrylic modified aromatic hydrocarbon. 78.5 parts of formaldehyde resin (Resin 1) were obtained.

  The weight average molecular weight, the ester value and the viscosity of the obtained resin 1 were measured. The results are shown in Table 2.

Example 2
Acrylic denatured aromatic in the same manner as in Example 1 except that K140E manufactured by Hudoh Co., Ltd. was used instead of K140 manufactured by Hudoh Co., Ltd. and 107.4 parts of methyl acrylate was blended instead of 150.7 parts. 88.7 parts of hydrocarbon formaldehyde resin (Resin 2) was obtained.

  The weight average molecular weight, the ester value and the viscosity of the obtained resin 2 were measured. The results are shown in Table 2.

[Example 3]
Acrylic denatured aromatic in the same manner as in Example 1 except using K100E manufactured by Hudoh Co., Ltd. instead of K140 manufactured by Hudoh Co., Ltd. and blending 107.4 parts of methyl acrylate instead of 150.7 parts 87.2 parts of hydrocarbon formaldehyde resin (Resin 3) was obtained.

  The weight average molecular weight, the ester value and the viscosity of the obtained resin 3 were measured. The results are shown in Table 2.

Example A
78.7 parts of KDO E made by Hudoh Co., Ltd., 23 parts of acrylic acid, 0.31 parts of polymerization inhibitor A (hydroquinone made by Wako Pure Chemical Industries, Ltd.), 150 parts of toluene, thermometer, Dean Stark device and dry air It was charged into a 500 ml reaction flask equipped with a flowing glass tube. 1.3 parts of para-toluenesulfonic acid (PTA, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction mixture with stirring. The reaction mixture was heated to reflux at 115 ° C. under normal pressure with stirring to remove water from the reaction system. The reaction time was 5 hours. After completion of the reaction, the reaction product is diluted with 150 parts of toluene and then washed with a 20% aqueous solution of sodium hydroxide to remove the catalyst and polymerization inhibitor, and finally the toluene is removed by distillation under reduced pressure to obtain an acrylic modified aromatic hydrocarbon formaldehyde resin (Resin A) 86.7 parts were obtained.

  The weight average molecular weight, the ester number and the viscosity of the obtained resin A were measured. The results are shown in Table 3.

Example B
An acrylic-modified aromatic hydrocarbon formaldehyde resin (resin B) was obtained in the same manner as in Example B except that 0.26 parts of a para-toluenesulfonic acid was blended instead of 1.3 parts, to obtain 69.2 parts. .

  The weight average molecular weight, the ester value and the viscosity of the obtained resin B were measured. The results are shown in Table 3.

Example C
An acrylic modified aromatic hydrocarbon formaldehyde resin (a resin (resin) in the same manner as in Example C except that a polymerization inhibitor B (p-methoxyphenol manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of the polymerization inhibitor A (hydroquinone) C) Obtained 77.1 parts.

  The weight average molecular weight, the ester value and the viscosity of the obtained resin C were measured. The results are shown in Table 3.

Example D
Acrylic-modified aromatic in the same manner as Example D except that 0.1 part of polymerization inhibitor C (copper chloride, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of 0.31 part of polymerization inhibitor A (hydroquinone). 84.9 parts of a group hydrocarbon formaldehyde resin (Resin D) were obtained.

  The weight average molecular weight, the ester number and the viscosity of the obtained resin D were measured. The results are shown in Table 3.

Example X
Twenty parts of the acryl-modified aromatic hydrocarbon formaldehyde resin obtained in Example 3 and 0.6 parts of a polymerization initiator (IRGACURE (registered trademark) 184 manufactured by BASF Corp.) were mixed to obtain a compounded composition.

Subsequently, this compounded composition is coated on a polyethylene terephthalate film (E5100 manufactured by Toyobo Co., Ltd., PET film) using a bar coater, and tack is applied under the condition of 250 mJ / cm ² using an ultraviolet irradiation device (high pressure mercury lamp). Repeated UV irradiation was performed until it disappeared, to obtain a cured coating. The cured film was measured for curability, rubbing test, curl, yellow index (YI), haze (Haze), total light transmittance (TT), elongation, chemical resistance and adhesion. The The results are shown in Table 4.

Example Y
A composition is prepared in the same manner as in Example X, except that the acrylic modified aromatic hydrocarbon formaldehyde resin obtained in Example 2 is blended instead of the acrylic modified aromatic hydrocarbon formaldehyde resin obtained in Example 3. I got a thing.

  Subsequently, a cured coating film was obtained in the same manner as in Example X for this blended composition. The cured film was measured for curability, rubbing test, curl, yellow index (YI), haze (Haze), total light transmittance (TT), elongation, chemical resistance and adhesion. The The results are shown in Table 4.

Comparative Example a
Twenty parts of Acrylate A (A-HD-N, hexanediol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.6 parts of a polymerization initiator (IRGACURE 184 manufactured by BASF Corporation) were mixed to obtain a compounded composition.

  Subsequently, a cured coating film was obtained in the same manner as in Example X for this blended composition. The cured film was measured for curability, rubbing test, curl, yellow index (YI), haze (Haze), total light transmittance (TT), elongation, chemical resistance and adhesion. The The results are shown in Table 4.

Comparative Example b
In the same manner as Comparative Example a except that instead of Acrylate A, Acrylate B (A-PTMG-65 manufactured by Shin-Nakamura Chemical Co., Ltd., polytetramethylene glycol (# 650) diacrylate) was blended, the blended composition was Obtained.

  Subsequently, a cured coating film was obtained in the same manner as in Example X for this blended composition. The cured film was measured for curability, rubbing test, curl, yellow index (YI), haze (Haze), total light transmittance (TT), elongation, chemical resistance and adhesion. The The results are shown in Table 4.

Comparative Example c
The same as Comparative Example a except that instead of Acrylate A, Acrylate C (A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd., 2,2-bis [4- (acroxydiethoxy) phenyl] propane) was blended Then, the compounded composition was obtained.

  Subsequently, a cured coating film was obtained in the same manner as in Example X for this blended composition. The cured film was measured for curability, rubbing test, curling, chemical resistance and adhesion. The yellow index (YI), the haze, the total light transmittance (TT) and the elongation could not be measured because of the large curl. The results are shown in Table 4.

  The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin of the present embodiment is applicable to various applications such as paints and coatings, inks, adhesives and adhesives, lenses, films for displays, and is extremely useful.

Claims (15)

  (Meth) acrylic-modified aromatic hydrocarbon formaldehyde resin obtained by subjecting a polyol-modified aromatic hydrocarbon-formaldehyde resin and (meth) acrylic acid or a derivative thereof to an esterification reaction.   The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to claim 1, having a weight average molecular weight (Mw) of 300 to 10,000.   The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to claim 1 or 2, which has an ester value of 20 to 850 mg KOH / g.   The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of claims 1 to 3, which has a viscosity at 25 ° C of 1,000 Pa · s or less.   The (meth) acryl modified aromatic hydrocarbon formaldehyde resin according to any one of claims 1 to 4, wherein the polyol modified aromatic hydrocarbon formaldehyde resin comprises a polyol modified xylene resin.   The (meth) acrylic-modified aroma according to any one of claims 1 to 5, wherein the polyol-modified aromatic hydrocarbon formaldehyde resin is obtained by reacting an aromatic hydrocarbon formaldehyde resin and a polyol under an acidic catalyst. Group hydrocarbon formaldehyde resin.   The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of claims 1 to 6, wherein a hydroxyl value of the polyol-modified aromatic hydrocarbon formaldehyde resin is 20 to 850 mg KOH / g.   The (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of claims 1 to 7, wherein the weight-average molecular weight (Mw) of the polyol-modified aromatic hydrocarbon formaldehyde resin is 250 to 10,000. .   A composition comprising the (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to any one of claims 1 to 8.   Hardened | cured material obtained by hardening | curing the composition of Claim 9.   Hardened | cured material obtained by hardening | curing the (meth) acryl modified aromatic hydrocarbon formaldehyde resin as described in any one of Claims 1-8.   The manufacturing method of the (meth) acryl modified aromatic hydrocarbon formaldehyde resin including the process of esterifying polyol modified aromatic hydrocarbon formaldehyde resin, and (meth) acrylic acid or its derivative (s).   The method for producing a (meth) acrylic-modified aromatic hydrocarbon formaldehyde resin according to claim 12, comprising the step of dehydration esterification of the polyol-modified aromatic hydrocarbon formaldehyde resin and the (meth) acrylic acid under an acid catalyst. .   The manufacturing of the (meth) acryl modified aromatic hydrocarbon formaldehyde resin according to claim 12, comprising the step of esterifying the polyol modified aromatic hydrocarbon formaldehyde resin and the (meth) acrylic acid derivative under an ester exchange catalyst. Method.   The manufacturing method of the (meth) acryl modified aromatic hydrocarbon formaldehyde resin of Claim 12 or 14 in which the said (meth) acrylic acid derivative contains a (meth) acrylic-acid alkylester.