WO2023149474A1 - Hydrogenated terpene-polyphenol copolymer resin and adhesive composition containing said copolymer resin - Google Patents

Abstract

Provided are: a terpene-based resin which has excellent adhesion to highly polar adherends such as glass, and which has high transparency and good weather resistance; and an adhesive composition using the same.　Provided are: a hydrogenated terpene-polyphenol copolymer resin obtained by hydrogenating a terpene-polyphenol copolymer resin which can be obtained by polymerizing a terpene-based compound and a polyphenol-based compound; and an adhesive composition obtained by mixing the hydrogenated terpene-polyphenol copolymer resin with a base polymer.

Description

Hydrogenated terpene polyhydric phenol copolymer resin and adhesive composition containing the copolymer resin

The present invention relates to a hydrogenated terpene polyhydric phenol copolymer resin and an adhesive composition containing the copolymer resin.

Terpene phenolic resin is a liquid or resinous compound obtained by copolymerizing terpene, an essential oil extracted from pine trees and citrus peels, with phenol. There are various products on the market that differ from each other in terms of , softening point, glass transition temperature, and the like.

By blending these resins into polymeric materials such as rubber and thermoplastic elastomers, the viscoelasticity and polarity of the polymeric materials can be adjusted. Utilizing this property, it is used in various fields such as adhesives, adhesives, rubber products such as tires, polymer modifiers, and dispersibility improvers.

For example, in the field of pressure-sensitive adhesives, terpene phenolic resin is added as a tackifying resin to acrylic pressure-sensitive adhesives based on acrylic polymers for the purpose of improving the adhesion to low-polar adherends such as polyolefins. is known (for example, Patent Documents 1 and 2). However, the addition of terpene phenolic resins leads to deterioration of the weather resistance and transparency that characterize acrylic pressure-sensitive adhesives. was sometimes shunned.

In view of the above, the present applicant has proposed the use of a hydrogenated terpene phenolic resin obtained by subjecting a terpene phenolic resin to a hydrogenation treatment as a tackifying resin for an acrylic pressure-sensitive adhesive (Patent Document 3). According to this document, by using a hydrogenated terpene phenolic resin, it is possible to improve the adhesion to low-polar adherends without deteriorating the weather resistance and transparency of the acrylic pressure-sensitive adhesive. On the other hand, with the trend toward lighter and thinner displays in recent years, the thickness of the adhesive layer is also becoming thinner, making it difficult to develop sufficient adhesive strength for adherends with high polarity such as glass. It's becoming

JP 2015-42729 A JP 2021-70744 A JP 2007-224258 A

An object of the present invention is to provide a novel terpene-based resin that is excellent in adhesive properties of adhesives, especially adhesive strength to highly polar adherends such as glass, and that is excellent in weather resistance and transparency. An object of the present invention is to provide a pressure sensitive adhesive composition.

The present inventors have found that a hydrogenated terpene-polyphenol copolymer resin obtained by copolymerizing a terpene-based compound and a polyhydric phenol-based compound is a highly polar adherend. It was found that it is useful as a tackifying resin for significantly improving the adhesive strength to and making it a pressure-sensitive adhesive having excellent weather resistance and transparency, and the present invention was completed.

That is, the present invention consists of claims 1 to 11 below.
<Claim 1>
A hydrogenated terpene-polyphenol copolymer resin obtained by hydrogenating a terpene-polyphenol copolymer resin obtained by copolymerizing a terpene-based compound and a polyhydric phenol-based compound.
<Claim 2>
The hydrogenated terpene polyhydric phenol covalent according to claim 1, wherein the terpene compound is at least one selected from the group consisting of α-pinene, β-pinene, limonene, dipentene, Δ3-carene, alloocimene, ocimene and myrcene. Polymeric resin.
<Claim 3>
3. The hydrogenated terpene polyhydric phenol copolymer resin according to claim 1 or 2, wherein the polyhydric phenol compound is represented by general formula (1).

(R1 is a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms; R2 is an alkyl or alkenyl group having 1 to 15 carbon atoms; n is an integer of 1 to 3; m is an integer of 0 to 2; and m are 3 or less.When n is 2 or more, two or more R1 may be the same or different.When m is 2 or more, two or more R2 may be the same or different. )
<Claim 4>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 3, wherein the polyhydric phenol compound is at least one selected from catechol, resorcinol, pyrogallol and guaiacol.
<Claim 5>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 4, wherein the copolymerization ratio of the terpene compound is 20 to 99 mol%.
<Claim 6>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 5, which has a polystyrene-equivalent weight average molecular weight (Mw) of 400 to 5,000 as measured by GPC (gel permeation chromatography).
<Claim 7>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 6, which has a softening point of 70 to 180°C.
<Claim 8>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 7, which has a hydroxyl value of 10 to 300 mgKOH/g.
<Claim 9>
The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 8, which has a hydrogenation rate of 5 to 100%.
<Claim 10>
The method for producing a hydrogenated terpene-polyphenol copolymer resin according to any one of claims 1 to 9, wherein a terpene-polyphenol copolymer resin obtained by copolymerizing a terpene-based compound and a polyhydric phenol-based compound is hydrogenated. .
<Claim 11>
A pressure sensitive adhesive composition comprising 1 to 300 parts by weight of the hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 9 with respect to 100 parts by weight of the base polymer.

The hydrogenated terpene polyhydric phenol copolymer resin of the present invention is excellent in the effect of modifying polymer materials such as rubber and thermoplastic elastomers. It can be used in various applications including the electronics field because it can be used as a pressure-sensitive adhesive with excellent transparency and heat stability.

1 is a GPC chart of a terpene polyhydric phenol copolymer resin of Production Example 1. FIG. 1 is a proton nuclear magnetic resonance (1H-NMR) spectrum of the terpene polyhydric phenol copolymer resin of Production Example 1. FIG. 4 is a GPC chart of the hydrogenated terpene polyhydric phenol copolymer resin of Production Example 4. FIG. 4 is a proton nuclear magnetic resonance (1H-NMR) spectrum of the hydrogenated terpene polyhydric phenol copolymer resin of Production Example 4. FIG.

Hereinafter, the present invention will be described for each component.
<Hydrogenated terpene polyhydric phenol copolymer resin>
The hydrogenated terpene polyhydric phenol copolymer resin of the present invention is a resinous compound obtained by hydrogenating a terpene polyhydric phenol copolymer resin obtained by copolymerizing a terpene compound and a polyhydric phenol compound. be.
First, the terpene polyhydric phenol copolymer resin will be described.

The above terpene compounds are hydrocarbons _{and their oxygen-containing derivatives in which a plurality of isoprene units represented by the molecular formula of C 5 H 8 are bonded .} It is classified into terpene (C ₅ H ₈ ) ₃ , diterpene (C ₅ H ₈ ) ₄ and the like. Of these, monoterpenes and sesquiterpenes are preferred.
Moreover, the terpene-based compound is preferably an alicyclic terpene having a carbon ring in the molecule. Furthermore, terpene hydrocarbons containing no heteroatoms such as hydroxyl groups in the molecule are preferred.

Specific examples of terpene compounds include α-pinene, β-pinene, 3-carene, camphene, tricyclene, limonene, dipentene, α-phellandrene, β-phellandrene, α-terpinene, β-terpinene, and γ-terpinene. , terpinolene, ocimene, alloocimene, myrcene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, γ-terpineol, linalool, longifolene, caryophyllene, farnesene and the like. Among these, α-pinene, β-pinene, 3-carene, limonene, dipentene, ocimene, alloocimene, myrcene, longifolene and caryophyllene are preferred, and α-pinene, β-pinene, 3-carene, limonene and dipentene are more preferred. . These can be used singly or in combination of two or more.

The above polyhydric phenol-based compound is a compound in which two or more hydrogen atoms of an aromatic hydrocarbon are substituted with a hydroxyl group or an alkoxy group, and is represented by general formula (1).

(R1 is a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms; R2 is an alkyl or alkenyl group having 1 to 15 carbon atoms; n is an integer of 1 to 3; m is an integer of 0 to 2; and m are 3 or less.When n is 2 or more, two or more R1 may be the same or different.When m is 2 or more, two or more R2 may be the same or different. )

Specific examples of polyhydric phenol compounds include catechol, resorcinol, hydroquinone, guaiacol, p-methoxyphenol, m-methoxyphenol, pyrogallol, phloroglucinol, eugenol, and propylcatechol. These can be used singly or in combination of two or more.

Catechol, guaiacol, pyrogallol and the like are known to be collected or derived from renewable natural resources. In recent years, there is concern about global warming due to depletion of petroleum resources and an increase in carbon dioxide emissions, so it is preferable to use such plant-derived polyhydric phenol compounds. In the terpene-polyphenol copolymer resin of the present invention, the terpene-based compound, which is a copolymer component, is also usually a plant-derived essential oil component, so by using it in combination with the plant-derived polyhydric phenol-based compound, the biomass degree It is possible to provide materials with high environmental load and low environmental impact.
For example, pyrogallol is found in a wide variety of plants, including quintuple (nurde galls), galls (middle eastern beech and oak galls), witch-hazel, tea leaves, and oak bark. It can be produced by decarboxylation from contained gallic acid. Moreover, it is known that catechol can be produced by a microbial fermentation method using plant-derived sugar as a raw material.

The terpene polyhydric phenol copolymer resin is selected from the group of monohydric phenol compounds and vinyl compounds as copolymerization components other than terpene compounds and polyhydric phenol compounds within a range that does not impair the effects of the present invention. At least one other monomer may be copolymerized at a total copolymerization ratio of about 50 mol % or less.

A monohydric phenol compound is a compound in which one hydrogen atom of an aromatic hydrocarbon is substituted with a hydroxyl group or an alkoxy group, and specifically includes phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, and octylphenol. , nonylphenol, decylphenol, thymol, carvacrol and the like. These can be used singly or in combination of two or more.

Vinyl compounds include ethylene, propylene, butylene, butadiene, isoprene, piperylene, cyclopentadiene, hexene, vinyl acetate, vinyl chloride, styrene, α-methylstyrene, coumarone, indene, vinyltoluene, isopropenyltoluene, divinylbenzene, Examples include divinyltoluene, 2-phenyl-2-butene, vinylnaphthalene and the like. Styrene, α-methylstyrene, etc. are preferred, and may be used alone or in combination of two or more.

The method for synthesizing the terpene polyhydric phenol copolymer resin is not particularly limited, and can be carried out based on a known method for synthesizing a terpene phenol resin except that phenol is replaced with a polyhydric phenol compound. For example, in an organic solvent, in the presence of a Friedel-Crafts catalyst, a terpene-based compound and a polyhydric phenol-based compound and optionally other monomers are dropped individually or mixed and added dropwise to a predetermined temperature and It can be produced by reacting for a period of time, and then removing the catalyst, unreacted monomers, solvent, etc. by washing with water, distillation, or the like, if necessary.

The ratio of the terpene-based compound and the polyhydric phenol-based compound used in the synthesis of the terpene-polyphenol copolymer resin is not particularly limited, but the ratio of the terpene-based compound to the total amount of the terpene-based compound and the polyhydric phenol-based compound is 20 to 99 mol % is preferred, 40 to 95 mol % is more preferred, and 50 to 90 mol % is even more preferred. If it is less than 20 mol %, the resin yield may become too low, and if it exceeds 99 mol %, the polyhydric phenol structure in the resin may be too small and desired properties may not be exhibited, which is not preferable.

Examples of the catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, aluminum chloride, iron chloride, zinc chloride, Copper chloride, boron trifluoride, boron trifluoride ether complex, boron trifluoride phenol complex, solid phosphoric acid, activated clay, zeolite, cation exchange resins, etc. may be mentioned, but not limited to these.

The amount of the catalyst used is 0.01 to 20% by weight, preferably 1 to 10% by weight, based on the raw material monomer when the reaction is a batch method. If the amount of the catalyst is less than 0.01% by weight, the reaction yield will be extremely low.

In addition, a reaction solvent may not be used, but a solvent may be used for the purpose of suppressing heat generation accompanying the polymerization reaction and allowing the reaction to proceed gently. The solvent is not particularly limited as long as it does not inhibit polymerization. , aromatic hydrocarbons such as toluene, xylene, cumene and cymene; and ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane.

The amount of solvent used is preferably 500% by weight or less, more preferably 300% by weight or less, based on the total amount of the terpene-based compound and the polyhydric phenol-based compound as raw materials. If the amount of the solvent exceeds 500% by weight, the batch efficiency is lowered and the manufacturing cost is increased, which is not preferable.

The reaction temperature is appropriately selected in consideration of the activity of the catalyst to be used, the boiling point of the solvent, etc., but it is usually -20 to 150°C, preferably 0 to 100°C. If the temperature is less than -20°C, the reaction becomes extremely slow. In particular, when aluminum chloride or boron trifluoride is used as a catalyst, the reaction temperature is preferably 0°C to 80°C, more preferably 10°C to 60°C.

The weight average molecular weight (Mw) of the terpene polyhydric phenol copolymer resin thus obtained is usually 400 to 5,000, preferably 500 to 4,000, more preferably 600 to 3,000. If the Mw is less than 400, the handling of the resin itself becomes poor, and there is concern about bleeding out after being made into a compound. On the other hand, if the Mw exceeds 5,000, it may become extremely difficult to dissolve in rubber or thermoplastic elastomer, which is not preferable.
The average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) using standard polystyrene as a standard substance.

The softening point of the terpene polyhydric phenol copolymer resin is not particularly limited, but is preferably 70 to 180°C, more preferably 80 to 160°C, still more preferably 100 to 140°C. If the softening point is less than 70°C, there is concern about bleeding out after being made into a compound. On the other hand, if the softening point exceeds 180° C., it may become extremely difficult to dissolve in rubber or thermoplastic elastomer, which is not preferable.
In addition, the softening point in this specification is a softening point measured by JIS K2207 ring and ball method.

The hydroxyl value of the terpene polyhydric phenol copolymer resin is usually in the range of 10-300 mgKOH/g, preferably 20-250 mgKOH/g. If the hydroxyl value is less than 10 mgKOH/g, a sufficient effect of modifying rubber or thermoplastic elastomer may not be obtained. On the other hand, when the hydroxyl value exceeds 300 mgKOH/g, compatibility deteriorates.
In addition, the hydroxyl value in the present specification is a hydroxyl value measured according to JIS K0070 7.1 Neutralization Titration Method.

Next, the hydrogenation (hydrogenation) of the terpene polyhydric phenol copolymer resin obtained by the above method will be described.
The hydrogenation method is not particularly limited, and can be carried out by a known method.
For example, in the presence of a hydrogenation catalyst, the terpene polyhydric phenol copolymer resin is usually heated under hydrogen pressure of 1 to 25 MPa, preferably 3 to 20 MPa, for 0.5 to 24 hours, preferably 1 to 10 hours. do it by

Examples of hydrogenation catalysts include metal catalysts such as palladium, ruthenium, rhodium, platinum, and nickel, and supported catalysts in which these are supported on carriers such as activated carbon, activated alumina, and diatomaceous earth. At this time, it is possible to use a batch system in which the reaction is carried out while stirring the powdered catalyst in suspension, or a continuous system using a reaction tower filled with a molded catalyst, and there is no particular limitation on the reaction system. do not have.

The amount of the hydrogenation catalyst used is 0.1 to 30% by weight, preferably 1 to 20% by weight, based on the raw material (terpene polyhydric phenol copolymer resin) when the reaction is a batch system. If the amount of the catalyst is less than 0.1% by weight, the reaction rate will be extremely slow.

A reaction solvent may not be used during hydrogenation, but alcohols, ethers, esters, and saturated hydrocarbons are usually preferably used. The amount of the reaction solvent used is generally 10 to 500% by weight, preferably about 50 to 300% by weight, based on the raw materials.

The reaction temperature during hydrogenation is not particularly limited, but is usually 0 to 300°C, preferably 50 to 250°C. If the reaction temperature is less than 0°C, the reaction rate will be significantly slowed. On the other hand, if it exceeds 300°C, the decomposition of the hydrogenated product will increase and the yield of the desired resin may decrease.

In the above hydrogenation reaction, hydrogen is added to the double bond in the terpene polyhydric phenol copolymer resin to form a carbon-carbon single bond. The double bond includes a double bond of an aromatic ring derived from polyhydric phenol and the like. The hydrogenation rate of double bonds is 5% or more, preferably 10% or more, more preferably 20% or more. Also, the hydrogenation rate of the aromatic ring is 0.5% or more, preferably 1% or more. The higher the degree of hydrogenation of the double bonds, the higher the transparency and oxidation stability of the resin, which can be preferably used in applications requiring transparency such as optical materials. On the other hand, if the hydrogenation rate of double bonds is less than 5%, the hue of the resin is poor, or the oxidation stability is not sufficiently exhibited.

Here, the hydrogenation rate (hydrogenation rate) of the double bond is a value calculated by the following formula from each integrated value of the peak derived from the double bond by ¹ H-NMR (proton NMR).
Hydrogenation rate (%) = {(AB) / A} × 100
A: Integral value of double bond peak before hydrogenation B: Integral value of double bond peak after hydrogenation

The weight average molecular weight (Mw) of the hydrogenated terpene polyhydric phenol copolymer resin is usually 400 to 5,000, preferably 500 to 4,000, more preferably 600 to 3,000. If the Mw is less than 400, the handling of the resin itself becomes poor, and there is concern about bleeding out after being made into a compound. On the other hand, if the Mw exceeds 5,000, it may become extremely difficult to dissolve in rubber or thermoplastic elastomer, which is not preferable.

Although the softening point of the hydrogenated terpene polyhydric phenol copolymer resin is not particularly limited, it is preferably 70 to 180°C, more preferably 80 to 160°C, and still more preferably 100 to 140°C. If the softening point is less than 70° C., handling of the resin itself becomes poor, and there is concern about bleeding out after being made into a compound. On the other hand, if the softening point exceeds 180° C., it may become extremely difficult to dissolve in rubber or thermoplastic elastomer, which is not preferable.

The hydroxyl value of the hydrogenated terpene polyhydric phenol copolymer resin varies depending on the type of elastomer to be mixed, but is usually in the range of 10 to 300 mgKOH/g, preferably 20 to 250 mgKOH/g, and more. Preferably it is 40-210 mgKOH/g. If the hydroxyl value is less than 10 mgKOH/g, it may not be possible to exhibit sufficient adhesion and adhesion properties to highly polar adherends such as metals and glass, which is not preferable. On the other hand, if the hydroxyl value exceeds 300 mgKOH/g, it may become extremely difficult to dissolve in low-polarity elastomers such as rubber.

Various additives such as known phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants can be added to the hydrogenated terpene polyhydric phenol copolymer resin of the present invention.

<Adhesive composition>
The hydrogenated terpene polyhydric phenol copolymer resin can be blended with a base polymer such as natural rubber or thermoplastic elastomer and used as an adhesive composition.

Thermoplastic elastomers that can be used as base polymers are not particularly limited, but examples include styrene-isoprene-styrene block copolymers, styrene-butadiene-styrene block copolymers, and styrene-ethylene-butylene-styrene block copolymers. , styrene-based block copolymers such as styrene-ethylene-propylene-styrene block copolymers, ethylene-vinyl acetate copolymers, (meth)acrylic copolymers, and the like. Among these, a (meth)acrylic polymer is particularly preferable from the viewpoint of compatibility.

A (meth)acrylic polymer is a polymer obtained by polymerizing a polymerizable monomer containing at least an alkyl (meth)acrylate. The types of alkyl (meth)acrylates are not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (amyl) (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (dodecyl) (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, etc. is mentioned.
In addition, "(meth)acrylate" means "acrylate" or "methacrylate" in this specification. The alkyl (meth)acrylates may be used alone, or two or more of them may be used in combination.

Moreover, a copolymerizable polar group-containing vinyl monomer may be further contained as a polymerizable monomer other than the alkyl (meth)acrylate.
As will be described later, the polar group-containing vinyl monomer effectively forms a crosslinked structure with a crosslinker having a specific functional group such as an isocyanate crosslinker, an epoxy crosslinker, and an aziridine crosslinker to form a cohesive force. It is used to achieve compatibility with repulsion resistance and, if necessary, to adjust the Tg, tackiness, etc. of the copolymer.

Specific examples of polar group-containing vinyl monomers include styrene-based monomers such as styrene, α-methylstyrene, o-methylstyrene and p-methylstyrene; carboxylic acid vinyl esters such as vinyl acetate; (meth)acrylic acid and itaconic acid. Carboxylic acid containing a vinyl group such as; anhydride of the carboxylic acid having a vinyl group; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone modification vinyl monomers having a hydroxyl group such as (meth)acrylate, polyoxyethylene (meth)acrylate, polyoxypropylene (meth)acrylate; nitrogen-containing vinyl monomers such as (meth)acryloylmorpholine, (meth)acrylamide, dimethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminomethyl(meth)acrylate; .
The above polar group-containing vinyl monomers may be used alone, or two or more of them may be used in combination.

Furthermore, in the present invention, by blending a small amount of polyfunctional (meth)acrylate into the base polymer, crosslinking can be carried out simultaneously with the polymerization of the acrylic copolymer.
Examples of such polyfunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, (Poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, glycerin methacrylate acrylate, pentaerythritol tri(meth)acrylate , trimethylolpropane trimethacrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy (meth)acrylate, polyester (meth)acrylate and urethane (meth)acrylate. These may be used alone or in combination of two or more.
The amount of the polyfunctional (meth)acrylate compounded is usually 0 to 5 parts by weight with respect to 100 parts by weight of the acrylic copolymer.

The (meth)acrylic polymer can be produced by (co)polymerizing at least one alkyl (meth)acrylate and other polymerizable monomers. Although the mode of the polymerization reaction is not particularly limited, radical polymerization or anionic polymerization is preferred. As the polymerization method, conventionally known methods such as bulk polymerization method, solution polymerization method, suspension polymerization method and emulsion polymerization method can be used, and the solution polymerization method and bulk polymerization method are preferable.
Moreover, when two or more types of polymerizable monomers are copolymerized, the sequence of the monomers is not particularly limited, and may be random, alternating, or block.

In the case of radical polymerization, if necessary, peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide, azo polymerization initiators such as azobisisobutylnitrile, etc., as well as photopolymerization initiators such as acetophenone polymerization Initiators such as benzoin ether-based polymerization initiators, benzyl ketal-based polymerization initiators, acylphosphine oxide-based polymerization initiators, benzoin-based polymerization initiators, and benzophenone-based polymerization initiators can be used.

On the other hand, polymerization initiators for anionic polymerization include alkali metals such as lithium, sodium and potassium, alkyllithium compounds such as methyllithium, ethyllithium, n-butyllithium, s-butyllithium and t-butyllithium, and lithium-naphthalene complexes. , sodium-naphthalene complexes, potassium-naphthalene complexes and other alkali metal-naphthalene complexes, as well as Grignard reagents, ketyl anion radical complexes, enolate anions, alkoxide anions such as t-butoxypotassium, lithium aluminum hydride, and the like. .
The amount of the polymerization initiator to be used is not particularly limited, but is usually 0 to 5 parts by weight per 100 parts by weight of the total amount of polymerizable monomers used.

A solvent in the polymerization reaction does not have to be used in particular, but a solvent may be used for the purpose of suppressing the viscosity increase of the reaction solution and facilitating temperature control during the reaction. Esters such as ethyl acetate and methyl acetate, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, and butanol, aliphatic hydrocarbons such as cyclohexane, hexane, and heptane, and aromatic hydrocarbons such as toluene and xylene. There are types. On the other hand, in anionic polymerization, in addition to aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, diethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, 1,2 Ethers such as dimethoxyethane and anisole, tertiary amines such as triethylamine and pyridine, and aprotic polar solvents such as N,N-dimethylformamide and N,N-dimethylacetamide can be used. These solvents may be used singly or in combination of two or more.

The (meth)acrylic polymer obtained by the above method preferably has a weight average molecular weight of 300,000 to 3,000,000 in terms of standard polystyrene measured by gel permeation chromatography (GPC). , 500,000 to 2,500,000.

The adhesive composition of the present invention contains 1 to 300 parts by weight, preferably 5 to 100 parts by weight, more preferably 5 to 100 parts by weight of the hydrogenated terpene polyhydric phenol copolymer resin of the present invention with respect to 100 parts by weight of the base polymer. It is blended at a ratio of 10 to 60 parts by weight. If the hydrogenated terpene polyhydric phenol copolymer resin is less than 1 part by weight, the effect of blending the hydrogenated terpene polyhydric phenol copolymer resin becomes difficult to understand. On the other hand, if it exceeds 300 parts by weight, the viscosity of the pressure-sensitive adhesive becomes too high, and the balance of adhesive properties such as ball tack, adhesive strength, and holding power deteriorates.

The adhesive composition of the present invention may contain a cross-linking agent as necessary. Examples of cross-linking agents include polyisocyanates, epoxy resins, polycarbodiimide compounds, aziridine compounds, polyvalent metal salts, metal chelates, and the like. By using at least one of these cross-linking agents, it is possible to improve the cohesive strength by bonding with polymer chains and other compounding agents, and to increase the holding power and constant load at high temperatures.

The content of the cross-linking agent varies depending on its type, but is usually in the range of 0.005 to 10 parts by weight, preferably 1.0 to 5 parts by weight, per 100 parts by weight of the (meth)acrylic polymer. Department. If the amount of the cross-linking agent is less than 0.005 parts by weight, the heat resistance may be insufficient, and the adhesion to the adherend may be lowered. On the other hand, if it exceeds 10 parts by weight, the cross-linking tends to be excessive, the flexibility tends to decrease, the adhesion to the adherend tends to decrease, and the peel strength tends to be insufficient. In addition, the excessive cross-linking agent may deteriorate adhesive properties.

When using a cross-linking agent, the adhesive composition of the present invention preferably undergoes a heating step to form a cross-linked structure. The heating step may be performed before or after application to the adherend. When used as a tape in which an adhesive layer is laminated on a substrate, it is preferable from the standpoint of production efficiency to heat the substrate after applying the adhesive composition. The heating temperature is appropriately set according to the type of cross-linking agent used, but is usually in the range of 40°C to 130°C, preferably 50°C to 100°C. The heating time is 30 minutes to 7 days, preferably 1 hour to 5 days.

The adhesive composition of the present invention may further contain plasticizers, softeners, pigments, fillers, diluents, anti-aging agents, UV absorbers, antioxidants, light stabilizers, surfactants, if necessary. Additives such as agents, release modifiers, and antistatic agents may be contained, and the form thereof may be any of solution type, water dispersion type, UV curing type, hot melt type, and the like.

The adhesive composition of the present invention can also be used by applying it to an adhesive sheet or adhesive tape. In this case, the support is not particularly limited, and for example, plastic film, paper, non-woven fabric, sheet or tape such as metal foil, plastic or rubber foam can be used.

The method of processing the adhesive composition of the present invention into the support is not particularly limited. For example, a method for producing a solvent-type acrylic pressure-sensitive adhesive composition containing an acrylic polymer as a main component includes an organic solvent such as toluene or ethyl acetate, an acrylic polymer and the hydrogenated terpene polyhydric phenol copolymer resin of the present invention, and A mixture of cross-linking agents is stirred and dissolved to prepare a sticky liquid having a solid content of 10 to 70% by weight. The pressure-sensitive adhesive composition prepared in this manner is applied to a support using, for example, a roll coater or a bar coater, and heated to volatilize the solvent to obtain a pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet. Although the thickness of the adhesive layer is not particularly limited, it is usually about 0.01 to 1.0 mm.

The adherend to which the pressure-sensitive adhesive composition of the present invention is applied is not particularly limited, and examples thereof include wood, metal, plastic, rubber, concrete, glass, tiles, ceramics, and composite materials. Among them, it is preferable because it can exhibit good adhesion and adhesion properties to highly polar adherends such as concrete, glass, tiles, and ceramics. Although the detailed principle is not clear, it is thought that multiple hydroxyl groups existing in close proximity in the structure of the hydrogenated terpene polyphenol copolymer resin form strong hydrogen bonds with the hydroxyl groups on the adherend. be done.

The adhesive composition of the present invention has high fixability to highly polar adherends such as glass. In addition, since it is excellent in heat resistance stability and transparency, it can be used in various fields such as the field of optics and electronics, the field of architecture, and the field of medicine including dentistry.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by the examples.
The softening point and hydroxyl value of the (hydrogenated) terpene polyhydric phenol copolymer resin were measured by the methods described in each measurement item in the specification. Further, the hydrogenation rate, molecular weight and hue were measured by the following methods.

(Hydrogenation rate)
A proton nuclear magnetic resonance (1H-NMR) spectrum was measured with a nuclear magnetic resonance apparatus AVANCE III 600 MHz (manufactured by BRUKER). 1,1,2,2-tetrachloroethane-d2 was used as the deuterated solvent. The degree of hydrogenation was calculated by the above formula from the integrated values of the double bond-derived peaks of each resin before and after hydrogenation.
(molecular weight)
Using gel permeation chromatography (GPC), the molecular weight in terms of standard polystyrene was measured. Differential refractometer WATERS2414 (manufactured by WATERS) was used as a detector, WATERS515 high performance liquid chromatography (manufactured by WATERS) as a pump, and TSK-gel G2000H8×2 and G3000HXL×1 (manufactured by TOSOH) as columns. Measurement conditions were as follows: tetrahydrofuran was used as an eluent, the flow rate was 1.0 mL/min, and 250 μL of sample solution with a sample concentration of 5 mg/mL was injected for measurement.
(hue)
10 g of the sample was dissolved in 10 g of toluene, and measured with a Gardner scale using a spectral color/haze meter COH7700 (manufactured by Nippon Denshoku Industries).

Production Example 1 (Production of terpene polyhydric phenol copolymer resin)
300 g of toluene, 55 g (0.5 mol) of catechol, and 20 g of boron trifluoride diethyl ether complex were introduced into a flask equipped with a stirrer, reflux condenser, thermometer, dropping pump and nitrogen gas inlet, and stirring was started. Into this, 272 g (2.0 mol) of α-pinene was added dropwise over 6 hours at a reaction temperature of 25 to 30°C. After dropping, the reaction mixture was allowed to react for 1 hour, then washed with water, and distilled at 245°C under reduced pressure of 3 mmHg to obtain 225 g of a reddish brown terpene polyhydric phenol copolymer resin having a softening point of 126°C. Mn (number average molecular weight), Mw (weight average molecular weight) and Mz (Z average molecular weight) were 610, 745 and 870, respectively. Further, the hydroxyl value was 120 mgKOH/g, and the hue (Gardner scale) was 14. The GPC chart and 1H-NMR chart of the obtained terpene polyhydric phenol copolymer resin are shown in FIGS. 1 and 2, respectively.

Production Example 2 (Production of hydrogenated terpene polyhydric phenol copolymer resin)
100 g of the terpene polyhydric phenol copolymer resin obtained in Production Example 1, 100 g of 2-propanol, and 5 g of a powdery 5% palladium-supported alumina catalyst were placed in an autoclave, which was then sealed and the atmosphere was replaced with hydrogen gas. After that, hydrogen gas was introduced while applying a pressure of 1 MPa. Then, when the mixture was heated to 180° C. with stirring, the hydrogen pressure was adjusted to 5 MPa, and the reaction was carried out for 1 hour while maintaining the pressure at 5 MPa by compensating for the absorbed hydrogen. After the reaction, the catalyst was filtered and 2-propanol was removed by distillation under reduced pressure to obtain 100 g of a hydrogenated terpene polyhydric phenol copolymer resin having a softening point of 130°C. The values of Mn, Mw and Mz were 620, 750 and 870, respectively. Further, the hydroxyl value was 119 mgKOH/g, the hue (Gardner scale) was 2, and the hydrogenation rate was 30%.

Production Examples 3-20
In the same manner as in Production Examples 1 and 2, except that the terpene compound used, the type of polyhydric phenol compound and their mixing ratio, and the hydrogenation time were changed as shown in Table 1, the copolymerization reaction and, if necessary, A hydrogenation reaction was carried out accordingly to obtain a resin having the properties described in each item in Table 1.
The GPC chart and 1H-NMR chart of the hydrogenated terpene polyhydric phenol copolymer resin obtained in Production Example 4 are shown in FIGS. 3 and 4, respectively.

Examples 1-15, Comparative Examples 1-9
(Evaluation of adhesive composition)
Per 100 parts by weight of an acrylic block copolymer (Clarity LA2140 (manufactured by Kuraray Co., Ltd.)), the (hydrogenated) terpene polyhydric phenol copolymer resin produced above, or 30 parts by weight of a commercially available tackifying resin, An acrylic adhesive composition was prepared by mixing 20 parts by weight of a liquid acrylic polymer (ALPHON UP-1061 (manufactured by Toagosei Co., Ltd.)) as a plasticizer. This pressure sensitive adhesive composition was coated on a 38 μm thick PET film so as to form a 30 μm thick pressure sensitive adhesive layer, and then dried to prepare a pressure sensitive adhesive sheet.

In addition, the following resin was used as a commercially available tackifying resin.
Comparative Example 6: Terpene Phenolic Resin A (YS Polyster T115, manufactured by Yasuhara Chemical Co., Ltd.)
Comparative Example 7: Terpene Phenolic Resin B (YS Polyster K125, manufactured by Yasuhara Chemical Co., Ltd.)
Comparative Example 8: Hydrogenated Terpene Phenolic Resin (YS Polyster NH, manufactured by Yasuhara Chemical Co., Ltd.)
Comparative Example 9: Rosin ester resin (Super Ester A100, manufactured by Arakawa Chemical Industries, Ltd.)

The resulting pressure-sensitive adhesive sheet was evaluated for loop tack (against SUS, glass, PE), adhesive strength (against SUS, glass, PE), holding power (against SUS, PE), and weather resistance by the methods described below. These results were as shown in Table 2.

(loop tuck)
A loop was formed with the adhesive surface of the test piece of the adhesive sheet facing outward, and a 25 mm×25 mm area was brought into close contact with the adherend, and the value when immediately pulled apart was measured with a tensile tester. The pulling speed was 300 mm/min, and the measurement temperature was 23°C.

(Adhesive force)
A sheet cut into a width of 25 mm and a length of about 200 mm was laminated to a SUS plate, glass plate or polyethylene (PE) plate by reciprocating a 2 kg roller twice in an atmosphere of 23°C. 180° peel adhesion was measured. A tensile tester was used for the measurement, and the tensile speed was 300 mm/min.

(Shear Adhesion Failure Temperature Test (SAFT))
A sheet cut into a width of 25 mm and a length of about 200 mm was attached to a SUS plate or a PE plate in an atmosphere of 23° C. by reciprocating a roller of 25 mm in length and 2 kg twice. After 30 minutes from bonding, it was allowed to stand in an atmosphere of 40° C. for 30 minutes, and then a load of 1 kg was applied. Simultaneously with applying the load, the temperature was raised at a rate of 2° C. for 5 minutes, and the temperature was read when the test piece dropped from the adherend.

(Weatherability)
Using a table sun XT750 manufactured by Suga Test Instruments Co., Ltd., the state of the adhesive was observed after irradiating the test piece with light of 48,000 lx for 100 hours in a 50° C. environment. When the adhesive turned yellow and cracked on the surface, it was evaluated as x, and when there was no change, it was evaluated as ◯.

 

As is clear from Table 2, when the hydrogenated terpene polyhydric phenol copolymer resin of the present invention is mixed with an acrylic pressure-sensitive adhesive, the weather resistance is better than that of an unhydrogenated terpene polyhydric phenol copolymer resin or the like. , and adhesive properties, especially tack and adhesion to glass, can be improved.

The hydrogenated terpene polyhydric phenol copolymer resin of the present invention is excellent in the effect of modifying rubber, thermoplastic elastomers, etc. It is useful as a pawn and the like.
In addition, polymer materials, polymer materials, compatibilizers, crystal nucleating agents, surface modifiers, filler dispersion improvers, fiber dispersion improvers, plasticizers, lubricants, curing agents, binders, oils and fats, traffic paints, It can be widely used in various applications such as inks, printing inks, toners, sizing agents, sizing agents, paper strength agents, road pavement compositions, civil engineering and construction materials, raw materials for polymer materials, modifiers, etc. have a useful effect on

Claims (11)

1. A hydrogenated terpene-polyphenol copolymer resin obtained by hydrogenating a terpene-polyphenol copolymer resin obtained by copolymerizing a terpene-based compound and a polyhydric phenol-based compound.
2. The hydrogenated terpene polyhydric phenol covalent according to claim 1, wherein the terpene compound is at least one selected from the group consisting of α-pinene, β-pinene, limonene, dipentene, Δ3-carene, alloocimene, ocimene and myrcene. Polymeric resin.
3. 3. The hydrogenated terpene polyhydric phenol copolymer resin according to claim 1 or 2, wherein the polyhydric phenol compound is represented by general formula (1).
   (R1 is a hydrogen atom or an alkyl or alkenyl group having 1 to 10 carbon atoms; R2 is an alkyl or alkenyl group having 1 to 15 carbon atoms; n is an integer of 1 to 3; m is an integer of 0 to 2; and m are 3 or less.When n is 2 or more, two or more R1 may be the same or different.When m is 2 or more, two or more R2 may be the same or different. )
4. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 3, wherein the polyhydric phenol compound is at least one selected from catechol, resorcinol, pyrogallol and guaiacol.
5. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 4, wherein the copolymerization ratio of the terpene compound is 20 to 99 mol%.
6. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 5, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the GPC (gel permeation chromatography) method is 400 to 5,000.
7. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 6, which has a softening point of 70 to 180°C.
8. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 7, which has a hydroxyl value of 10 to 300 mgKOH/g.
9. The hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 8, which has a hydrogenation rate of 5 to 100%.
10. The method for producing a hydrogenated terpene-polyphenol copolymer resin according to any one of claims 1 to 9, wherein a terpene-polyphenol copolymer resin obtained by copolymerizing a terpene-based compound and a polyhydric phenol-based compound is hydrogenated. .
11. A pressure sensitive adhesive composition comprising 1 to 300 parts by weight of the hydrogenated terpene polyhydric phenol copolymer resin according to any one of claims 1 to 9 with respect to 100 parts by weight of the base polymer.