JP2002322450A - Resin tackifier and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To newly develop a resin tackifier having a good color tone, easy polymerized and having excellent adhesive properties such as adhesion, cohesion power and tackifying ability. SOLUTION: This tackifier resin is obtained by polymerizing (A) 8-10C aromatic unsaturated hydrocarbons and (B) rosin esters prepared by esterifying at least one kind of rosins and rosin derivative with alcohols or further with (C) cyclic diolefins such as ethylidene norbornene, dipentene and dicyclopentadiene having no polar group. The resin exhibits excellent adhesive properties with a good balance among the cohesion power, the tackifying ability and retentivity by polymerizing the (A) and (B) or further (C), for example, compared with a resin in which the (A) and (B) are simply mixed. Adhesive properties to an polyolefin are improved by additionally polymerizing the (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tackifier resin and a method for producing the same, which is excellent in adhesive performance such as tackiness, cohesion, or tackiness regardless of materials such as metal, polyolefin and glass. Provide things.

[0002]

BACKGROUND OF THE INVENTION Generally, solvent-based adhesives, hot-melt adhesives, or pressure-sensitive adhesives include acrylics, natural rubbers, SBRs, SISs, and EVAs for improving adhesiveness.
A tackifier resin is added to various base polymers such as urethane, CR and the like. The tackifier resin includes petroleum-based, rosin-based, or terpene-based resins. By adding at least one of these resins to the base polymer, the viscosity of the system is reduced, and a plasticizing effect is imparted. To improve the wettability to the adherend, improve the bonding force at the interface between the adhesive and the adherend, and improve the adhesive properties.

[0003] Rosin-based tackifier resins are commonly used because of their excellent tackiness and compatibility with the base polymer. On the other hand, rosin-based tackifier resins tend to have poor adhesion holding power, weather resistance and heat stability. However, there is a problem in that it does not reach other tackifier resins in terms of the above. For example, as shown in U.S. Pat. No. 4,447,354, the stability can be improved by disproportionating rosin, but the improvement is still sufficient compared to petroleum-based tackifier resins. The same applies to the adhesive holding force.

On the other hand, aromatic petroleum resin is a tackifier resin of the petroleum (C ₉ petroleum resins), as compared to the rosin-based tackifier resin, light resistance, excellent heat stability, strong adhesive It has a holding power and is inexpensive compared to rosin, which is a natural product, so that it can be used widely. However, since the petroleum resin is composed of styrenes, there are problems in that the molecular structure is rigid, it is difficult to produce tackiness and tackiness, and the compatibility with the adhesive base polymer is poor. For this reason, in actual applications, both rosin-based and petroleum-based tackifier resins are often used in combination in order to compensate for the respective disadvantages.

[0005]

2. Description of the Related Art As described above, there are the following conventional techniques using a rosin-based and petroleum-based tackifier resin in combination. (1) JP-52-21048 JP (prior art 1) C ₅ based chain conjugated diene 40-90% by weight of an aliphatic
And petroleum resin obtained by cationic polymerization, tackifier resins obtained by mixing the rosin is disclosed a monomer mixture and styrene 60-10% by weight of C ₈ -C ₁₀ and. Compared to using rosin or petroleum resin alone,
A hot melt adhesive having much better adhesive performance and heat stability was obtained (see the upper right column on page 2 of the publication), and when an acid-modified or ester-modified petroleum resin was used, unmodified petroleum resin was used. It is described that the compatibility with an ethylene-based copolymer as a base polymer is improved as compared with the case (see the upper left column on page 4 of the publication).

(2) JP-A-52-108489 (Prior Art 2) When a petroleum fraction containing a hydrocarbon of C ₉ or more is thermally polymerized under high temperature and pressure, rosin and the like are added to polymerize. Then, a polar group is introduced into the resulting resin to improve the adhesiveness of the resin, and it is disclosed that the resin is suitable as a rubber tackifier resin (see the claims of the publication and the upper right column of page 2). .

(3) JP-A-53-6396 (Prior Art 3) A modified petroleum resin obtained by reacting two types of naphtha cracked oils having different boiling points with rosins in the presence of a catalyst is further treated with maleic anhydride. To produce a modified resin, and it is disclosed that a petroleum resin emulsion obtained by reacting the resulting modified resin with oils and fats is used for an adhesive or the like (Examples 4 and 3 of the same publication). (See upper right column).

[0008] (4) JP-A-4-175324 discloses (prior art 4) in the presence of an adduct of rosin and an aldehyde, by reacting a petroleum resin and polyhydric alcohols consisting of C ₅ based or C ₉ based Rosin-modified petroleum resin is disclosed (claims in the publication,
And Examples 1 to 3) that the obtained rosin-modified petroleum resin can be used as a binder to produce a lithographic printing ink excellent in high-speed printing suitability.
(Refer to the right column on page 1 of the publication and the item of the effect of the invention).

(5) JP-A-4-33905 (Prior Art 5) A rosin is added to a raw oil containing indene and polymerized with an acid catalyst to produce a rosin-modified indene resin. A specific indene resin obtained by hydrogenating a modified indene resin is disclosed (see the claims of the publication and the lower left column to the upper right column on page 2).

(6) JP-A-55-90573 (Prior Art 6) A tackifier resin for an elastomer obtained by graft copolymerizing an aliphatic conjugated diene compound such as butadiene and isoprene with a C ₉ petroleum resin, or Tackifier resins for elastomers obtained by graft copolymerizing the aliphatic conjugated diene compound with rosin esters are disclosed (Examples 3 and 4 in Table 1 and Examples 7 and 8 in Table 2 of the same publication). reference).

[0011]

In the technique of simply mixing both rosin-based and petroleum-based tackifier resins as in the above-mentioned prior art 1, the adhesive performance is deteriorated unless rosins are used in an appropriate mixing ratio. And the compatibility with the base polymer deteriorates. The above prior arts 2 to 6 are intended to improve these problems, and instead of mixing various tackifier resins, polymerizing a rosin or the like and a petroleum fraction to obtain an adhesive performance, This is an example of an attempt to improve compatibility with a base polymer.

However, the tackifier resin of the prior art 2 has a poor color tone because rosins are used as a raw material.
Because only low softening points can be obtained, the range of use is narrow.
Conventional technologies 3 and 4 using rosins as raw materials are basically the same in that there is a possibility that the color tone may deteriorate. Further, in the above-mentioned prior art 5, the problem is improved by lightening by hydrogenation, but on the other hand, a special device is required for hydrogenation and productivity is reduced. The obtained rosin-modified indene resin is expensive and poor in versatility. Further, when rosins are used as a raw material as in the related arts 2 to 5, the copolymerizability with the monomer tends to be low, and there is a problem in the reaction yield.

On the other hand, in the above-mentioned prior art 6, instead of rosins, rosin esters are used to polymerize with aliphatic conjugated dienes such as isoprene and butadiene. Actually, the polymerizability has not been improved (see the copolymerization ratio in Comparative Example 6 described later).

The present invention has good color tone and polymerizability,
A technical task is to newly develop a tackifier resin having excellent adhesive properties such as adhesive strength, cohesive strength, and tackiness.

[0015]

The present inventors Means for Solving the Problems], said from the prior art 2-6, in particular, rosins and C ₈ -C ₁₀ aromatic polymerization intensive research result of unsaturated hydrocarbons, It has been found that the carboxyl group of rosins acts as a catalyst poison of the polymerization catalyst to lower the polymerization rate, or that the rosins themselves may be decarboxylated to induce the decomposition of rosins. Therefore, based on this finding, in place of the rosin, the carboxyl group is reacted rosin esters neutralized with alcohol C ₈ -C ₁₀ aromatic unsaturated hydrocarbons, more pale, the polymerizable Excellent, rosin-based, petroleum resin-based tackifier resin that has both excellent adhesive performance, etc. can be obtained. Also, by polymerizing a cyclic diolefin having no polar group as the third component, adhesion to polyolefin The performance is remarkably improved, and further, by performing these polymerization reactions under special conditions,
The inventors have found that the color tone can be lightened and the polymerizability can be further improved, and the present invention has been completed.

That is, the present invention 1 is a method of polymerizing (A) a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon and (B) a rosin ester obtained by esterifying at least one of a rosin and a rosin derivative with an alcohol. Is a tackifier resin obtained by the above method.

The present invention 2 comprises (A) a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon, (B) a rosin ester obtained by esterifying at least one of a rosin and a rosin derivative with an alcohol, and (C) ) Tackifier resin obtained by polymerizing a cyclic diolefin having no polar group.

In the present invention 3, the cyclic diolefin (C) according to the above-mentioned present invention 2, wherein the ethylenidene norbornene, ethylidene bicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, limonene , Dipentene and the like.

The present invention 4 provides a tackifier resin according to any one of the above-mentioned present inventions 1 to 3, wherein the alcohol is a dihydric to tetrahydric alcohol.

[0020] The present invention 5 is characterized in that, in any of the above invention 1 to 4, C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A) is,
The C ₉ petroleum fraction obtained by distillation purification, a tackifier resin, wherein the vinyl toluene content in the total monomers is a vinyl toluene-rich fraction from 40 to 80 wt%.

The present invention provides a rosin ester obtained by esterifying at least one of a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon (A) and a rosin or a rosin derivative with an alcohol.
A method for producing a tackifier resin by polymerizing (B) with (A) / (B) = 30 to 95% by weight / 70 to 5% by weight. This is a method for producing a resin.

The present invention provides a rosin ester obtained by esterifying a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon (A) and at least one of a rosin and a rosin derivative with an alcohol.
In the method for producing a tackifier resin by polymerizing (B) and a cyclic diolefin having no polar group (C), the cyclic diolefin (C) is polymerized at a ratio of 1 to 50% by weight. A method for producing a tackifier resin.

[0023] The present invention 8 relates to the invention 6 or 7, wherein the aromatic unsaturated hydrocarbon (A) and the rosin ester are used.
(B) or a cyclic diolefin (C) further added to (A) and (B), followed by polymerization in a nitrogen atmosphere.

In the ninth aspect of the present invention, the rosin ester (B) and the acid catalyst are dissolved in a solvent in which the aromatic unsaturated hydrocarbons (A) are added, The method for producing a tackifier resin is characterized in that a polymerization reaction is carried out by further adding a cyclic diolefin (C).

The present invention 10 is an acrylic, natural rubber,
An adhesive composition obtained by adding the tackifier resin of any of the present inventions 1 to 5 to a base polymer such as SBR, SIS, EVA, urethane, or CR.

[0026]

DETAILED DESCRIPTION OF THE INVENTION The present invention is primarily a tackifier resin obtained by polymerizing a C ₈ -C ₁₀ aromatic unsaturated hydrocarbons and rosin esters, in the second, further A third component is a tackifier resin obtained by polymerizing a cyclic diolefin having no polar group, third, a method for producing a tackifier resin by polymerizing these reactants under a nitrogen atmosphere, and fourthly. First, a method for producing a tackifier resin in which a rosin ester and an acid catalyst are dissolved in a solvent, and the remaining reactants are added to the solvent to carry out polymerization.Fifth, these tackifier resins are used. An adhesive composition added to a base polymer such as an acrylic resin.

As the rosin esters (B), at least one of rosins and rosin derivatives esterified with alcohols can be used alone or in combination. The rosins are abietic acid, parastolic acid, neoabietic acid, pimaric acid, isopimaric acid, or tall oil rosin containing a resin acid such as dehydroabietic acid as a main component,
Unmodified rosin such as gum rosin and wood rosin.
The rosin derivative is disproportionated rosin, polymerized rosin, hydrogenated rosin, or other chemically modified rosin, or unsaturated carboxylic acid-modified rosin.

The above-mentioned rosin esters are produced by a known esterification method of a rosin or a rosin derivative and an alcohol. In the esterification reaction, the charging ratio of the rosin or the rosin derivative to the alcohol is COOH / OH = 1 / 0.2 to 1.5 in terms of the hydroxyl equivalent of the alcohol to the carboxyl equivalent of the rosin. About 150-300 ° C, reaction time is 1-
About 30 hours is appropriate.

The alcohols used for the esterification include dihydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol and 1,6-hexanediol, and glycerin. Trihydric alcohols, tetrahydric alcohols such as pentaerythritol and dipentaerythritol, or triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine,
An amino alcohol such as N-n-butyldiethanolamine or the like can be used alone or in combination. As the alcohols, as shown in the present invention 4, 2- to 4-hydric alcohols are excellent in terms of reactivity with rosins or rosin derivatives and cost, and these polyhydric alcohols are rosin-based tackifiers. It has a track record of being widely used as an agent resin. However, although monohydric alcohols can be used as the above-mentioned alcohols, the esterification reaction yield is poor, and an alkyl chain is incorporated into the molecule, which may adversely affect the adhesive performance such as the adhesive holding power of the resin. Therefore, it is not very suitable for the present invention. Although the case where tetravalent is exceeded can be used, not only the esterification efficiency is poor due to steric hindrance, but also unreacted hydroxyl groups may remain excessively and polymerization may not be successful.

For the purpose of increasing the softening point of rosin esters, a modified rosin ester obtained by esterifying the above-mentioned unsaturated carboxylic acid-modified rosin can be used. The unsaturated carboxylic acid-modified rosin ester is specifically obtained by reacting a rosin with an alcohol and an α, β-unsaturated carboxylic acid sequentially or simultaneously. In this method of sequentially reacting, a rosin is first reacted with an α, β-unsaturated carboxylic acid to produce a modified rosin, and then an alcohol is reacted. At this time, the amount of the α, β-unsaturated carboxylic acid to be charged is suitably about 1 mol part of α, β-unsaturated carboxylic acid or less per 1 mol of rosin. α, β-unsaturated carboxylic acids are
To react by adding to the conjugated double bond site of rosin,
The extent of not impairing the copolymerizability with C ₈ -C ₁₀ aromatic unsaturated hydrocarbons, or to the extent that compatibility with the base polymer is not deteriorated as tackifier resin, even when the adjustment of the feed amount is required is there. The α, β-unsaturated carboxylic acids are α, β
-Unsaturated carboxylic acids or acid anhydrides thereof, and specific examples thereof include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride (anhydride), itaconic acid, and citraconic acid (anhydride).

The C ₈ -C ₁₀ aromatic unsaturated hydrocarbons of the above (A) are monomers having a boiling point of about 140 to 240 ° C., which are BTX-extracted from a heavy oil fraction obtained by pyrolysis of petroleum naphtha. Mainly having 8 to 10 carbon atoms, mainly 9 carbon atoms
O-, m-, p-vinyltoluene, α-, β-methylstyrene, indene, etc., and contains styrene, methylindene, dicyclopentadiene, etc. as other minor components. However, the concentration of all of these polymerizable monomers is about 40 to 60% of the whole. Usually, the above C ₈ -C ₁₀ aromatic unsaturated hydrocarbons
(A) contains about 20% by weight of vinyltoluene. In the present invention 5, the concentration of vinyltoluene is increased by subjecting it to precision distillation. A tackifier resin having a lighter color tone can be obtained without impairing the adhesive performance. Depending on the conditions of precision distillation, it is possible to further increase the vinyltoluene concentration. However, considering practical aspects such as cost, 40 to 80% by weight is appropriate, and preferably 50 to 70% by weight.

The tackifier resin of the present invention 1 has the above C
At ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A) and the rosin ester (B) and a solvent, room temperature to 1 in the presence of an acid catalyst
It is obtained by cationic polymerization at a reaction temperature of 00 ° C., and can have both excellent adhesiveness of an aromatic petroleum resin and excellent adhesiveness and tackiness of a rosin-based resin.
As shown in the present invention 6, the added amount of each raw material is C ₈ -C ₁₀
Aromatic unsaturated hydrocarbons (A) / rosin esters (B) =
30 to 95% by weight / 70 to 5% by weight, preferably 50%
-90% by weight / 50-10% by weight. Examples of the acid catalyst include Friedel-Crafts catalysts such as BF ₃ , AlCl ₃ , ZnCl ₂ , alumina, and zeolite. Preferably, BF ₃ is used. After the reaction, the catalyst is neutralized and removed with an alkali. As the solvent, a heavy solvent, an aromatic solvent, a ketone solvent, an ester solvent, or the like is used, and an aromatic solvent is most suitable. With heavy solvents, there is a problem that it is difficult to remove from the product by vacuum distillation after the completion of the reaction, and with the remaining solvents, there is a problem that it becomes a catalyst poison or the resin polymerized during the reaction is deposited without being completely dissolved There is.

Specific polymerization methods (A) and (B) include the following methods 1 to 3, and from the viewpoint of polymerization efficiency, polymerization method 3 is preferred (see the present invention 9). (1) Polymerization method 1: C ₈ -C ₁₀ aromatic unsaturated hydrocarbon feedstock
A method in which a rosin ester (B) is dissolved in (A) and reacted at a predetermined temperature while adding an appropriate amount of a catalyst. (2) Polymerization method 2: In a solvent containing a catalyst, the above (A) and (B)
A method for promoting polymerization by adding a dissolved substance of (3) Polymerization method 3: In a solvent in which the catalyst and the above (B) are dissolved,
A method of reacting by dropping (A). Further, as shown in the present invention 8, when this polymerization reaction is carried out in a nitrogen atmosphere, adverse effects such as oxidation and coloration of a polymer or a raw material or reduction of reactivity due to oxygen acting as a reaction inhibiting substance. Can be prevented.

The present invention 3 is a tackifier resin obtained by polymerizing a cyclic diolefin having no polar group (C) as a raw material in addition to the above (A) and (B). The main object of the present invention is to improve the polyolefin adhesion of the adherend while maintaining the properties of the tackifier resins of Nos. 1 to 2 above. The cyclic diolefins having no polar group (C) do not have a polar group such as a hydroxyl group, a sulfonic acid group and an amino group in the molecule,
Compounds having one or more cyclo rings and two double bonds, specifically, ethylidene norbornene, ethylidene bicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, cyclopentadiene, dicyclo Pentadiene, limonene, dipentene and the like can be used alone or in combination, and ethylidene norbornene, dicyclopentadiene, dipentene and the like are preferable.

The cyclic diolefins (C) may be originally contained in the C ₈ -C ₁₀ aromatic unsaturated hydrocarbons as raw materials, but in the present invention 2-3, they are separately extracted and produced. Alternatively, a copolymer obtained by newly adding the synthesized cyclic diolefins and using the three components (A), (B) and (C) as monomer components. Thus, although the production can be replaced all C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A) is the cyclic diolefins (C), in practice, as shown in the present invention 7 In addition, the addition amount of the above (C) is about 1 to 50% by weight, and considering cost, preferably 5 to 30% by weight.
% By weight. As a reaction procedure for polymerizing the above (A), (B) and (C), the cyclic diolefin (C) is not a rosin ester (B) but a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon. With rosin esters (A)
It is preferably added to the solvent in which (B) and the catalyst are dissolved (see Invention 9).

As shown in the tenth invention, the tackifier resin of the inventions 1 to 5 is made of acrylic, natural rubber, SBR
By adding it to various base polymers such as a system, a SIS system, an EVA system, a urethane system or a CR system, various adhesive compositions such as a solvent type, a hot melt type and a pressure sensitive type are constituted. For example, in a solvent-type pressure-sensitive adhesive obtained by adding the tackifier resin of the present invention 1 to 5 to an acrylic polymer, the addition ratio of the tackifier resin to 100 parts by weight of the acrylic polymer is generally about 1 to 40 parts by weight. , Preferably 3
About 25 parts by weight. In addition, in various adhesive compositions,
Needless to say, a curing agent, a plasticizer, a softening agent, a filler, an antifoaming agent, an antioxidant, a film-forming aid, a pigment, a water-proofing agent, and the like can be added as needed.

[0037]

[Action] is reacted C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A) and the rosin ester and (B) in the presence of an acid catalyst,
It becomes a copolymer via the unsaturated portions of each other. In particular, rosins are a mixture of various resin acids containing abietic acid as a main component, and the conjugated double bond of abietic acid greatly contributes to promotion of a polymerization reaction. This copolymer is different from the above-mentioned prior art 1 in which a C ₉ petroleum resin and a rosin resin are simply mixed, and the components of both tackifier resins are incorporated in one molecule, so that the base polymer or the like is not used. without being affected by conditions is estimated and adhesion and tackiness of the rosin-based resin, and that the cohesion of the C ₉ petroleum resin can be expressed simultaneously.

When a cyclic diolefin having no polar group (C) such as ethylidene norbornene is used as the third component as a copolymer raw material, non-polar polyethylene,
The affinity for polyolefins such as polypropylene can be increased, and the adhesiveness can be improved.

When the above (A) and (B), or (C) is further polymerized, when the polymer is reacted in the air, the polymer or the raw material is oxidized and colored, or the oxygen acts as a reaction inhibiting substance to cause a reaction. However, if the reaction is performed in a nitrogen atmosphere, these adverse effects can be avoided. In the above polymerization reaction, BF ₃
However, the carboxyl group of rosins acts as a catalyst poison for these polymerization catalysts, which may reduce the polymerization rate or cause decarboxylation of the rosin itself to induce the decomposition of rosin. In the present invention, in order to use rosin esters having a carboxyl group blocked with an alcohol,
The adverse effects of carboxyl groups can be avoided. However,
In general, the rosin esters (B) have low reactivity, and thus are not easily polymerized by rosin esters. However, the petroleum fraction (A) tends to form a homopolymer because of high reactivity. Therefore, when a petroleum fraction (A) is added to a rosin ester containing a catalyst during polymerization, the above (A)
It can be expected that the polymerization of the above (A) and (B) proceeds efficiently while suppressing the formation of homopolymers between them.

[0040]

[Effect of the Invention] (1) As shown in the test examples below, the tackifier resin of the present invention, because they are obtained by polymerizing C ₈ -C ₁₀ aromatic unsaturated hydrocarbons and rosin esters, solvent type When applied to various adhesives such as hot melt type, pressure sensitive type, etc., a mixture of C ₉ petroleum resin and rosin type resin according to the prior art 1 mentioned above, rosin esters and isoprene according to the prior art 6 etc. copolymers of conjugated dienes, or, as compared to copolymers of conventional C ₈ -C ₁₀ aromatic compliant with technical 2-5 unsaturated hydrocarbons and rosins, adhesive strength, tackiness In addition, there is no bias in cohesion, and excellent adhesive properties can be exhibited in all cases. Further, in place of the rosin and the polymerization of the rosin ester to C ₈ -C ₁₀ aromatic unsaturated hydrocarbons, more light color, it is possible to manufacture a highly polymerization rate tackifier resin. Therefore, the tackifier resin of the present invention in which rosin esters are polymerized on C ₈ -C ₁₀ aromatic unsaturated hydrocarbons is a petroleum resin and rosin-containing resin in terms of adhesive properties, lightening, and high polymerization rate. simple mixture, of course, copolymers of C ₈ -C ₁₀ aromatic unsaturated hydrocarbons and rosins, even compared to the copolymer of rosin ester and a conjugated diene, the advantage is obvious.

(2) In the present invention 2, since a cyclic diolefin having no polar group is polymerized as a third component, a predetermined component such as ethylidene norbornene can be used without deteriorating the adhesion to stainless steel, glass, etc. by the effect of copolymerization. The polyolefin adhesion can be remarkably improved by the effect of the cyclic diolefins.

(3) In the present invention 5, since a vinyl toluene-rich fraction is used for the C ₈ -C ₁₀ aromatic unsaturated hydrocarbons, the cause of coloring such as coloring conjugated diolefins, nitrogen compounds, sulfur compounds, etc. Can be removed, which can contribute more effectively to the lightening of the tackifier resin.

(4) In the ninth aspect of the present invention, in the solvent in which the polymerization catalyst and the rosin ester (B) are dissolved, the C ₈ -C ₁₀ aromatic unsaturated hydrocarbon (A) or the cyclic diolefin is further added. Kind
Since (C) is added, the polymerization of (A) and (B), and further, the polymerization of (C) can proceed efficiently while suppressing the formation of the homopolymer of (A). Further, in the present invention 8, since the above (A), (B) and (C) are polymerized in a nitrogen atmosphere, the tackifier resin can be effectively lightened.

[0044]

EXAMPLES Hereinafter, C ₈ -C ₁₀ aromatic unsaturated hydrocarbons,
Production examples of rosin esters, production examples of tackifier resin using the same, test examples of evaluation of adhesive performance of an adhesive using the tackifier resin, and the like will be sequentially described. In the examples and test examples below, “parts” and “%” are based on weight unless otherwise specified. It should be noted that the present invention is not limited to the following examples and test examples, and it is needless to say that any modifications can be made within the technical idea of the present invention.

<< Production Example of C ₈ -C ₁₀ Aromatic Unsaturated Hydrocarbons >> A C ₆ -C ₁₁ heavy oil-based petroleum fraction obtained by decomposing petroleum naphtha is extracted and distilled. As a result, C ₈
A C ₉ petroleum fraction, which is a C ₁₀ aromatic unsaturated hydrocarbon, was obtained. Then, the raw material was precision distilled to obtain a vinyltoluene-rich fraction having a monomer concentration of 70% in which 65% of all the monomers were vinyltoluene.

<< Production Example of Rosin Esters >> (1) Production Example 1 In a 2000 ml four-necked flask equipped with a stirrer and a thermometer, tall oil rosin (acid value 170, color number (USDA) WW
Melting 1000 parts under nitrogen atmosphere, 180 ° C
Then, 93 parts of glycerin was added, and the mixture was heated to 270 ° C. over 5 hours and reacted at the same temperature for 6 hours to obtain a rosin glycerin ester having an acid value of 20, a softening point of 85 ° C. and a color tone (Gardner) of 6. Was.

(2) Production Example 2 Based on Production Example 1 above, 1000 parts of tall oil rosin melted in a flask and 2 parts of maleic anhydride at 200 ° C.
After adding 0.5 part of glycerin and raising the temperature to 270 ° C over 5 hours, the mixture was reacted at the same temperature for 2 hours to obtain an acid value of 16, a softening point of 94 ° C and a color tone ( Gardner) 6. A maleic anhydride-modified rosin glycerin ester was obtained.

(3) Production Example 3 900 parts of tall oil rosin based on Production Example 1 above
100 parts of polymerized rosin (acid value 140, number of colors (USDA) WW class),
The mixture was heated to 270 ° C. using 91 parts of glycerin and reacted at that temperature for 5 hours to obtain an acid value of 19 and a softening point of 95.
A glycerin ester of rosin and polymerized rosin having a color number (Gardner) of 6.5 ° C. was obtained.

<< Examples of Production of Tackifier Resin >>
By polymerizing the aforementioned C ₈ -C ₁₀ aromatic unsaturated hydrocarbons and rosin esters were prepared various tackifier resins. Of the following Production Examples 1 to 9, Example 1 is an example in which a normal C ₉ petroleum fraction not subjected to precision distillation and a rosin glycerin ester are subjected to a polymerization reaction in a nitrogen atmosphere. Example 3 in which the vinyltoluene-rich fraction obtained in the above Production Example was used in place of the ordinary C ₉ petroleum fraction of Example 1, and Example 3 was obtained by polymerizing ethylidene norbornene as the third component in Example 1 further. Example 4, Example 4 is an example in which ethylidene norbornene is further polymerized as a third component in Example 2, Example 5 is an example in which the third component in Example 4 is replaced with dicyclopentadiene, and Example 6 is an example in which Example 2
Example 7 in which the rosin glycerin ester of Example 2 was replaced with the maleic anhydride-modified rosin ester of Preparation Example 2, Example 7 was an example in which the rosin glycerin ester of Example 2 was replaced with the glycerin ester of rosin and polymerized rosin of Preparation Example 3,
Example 8 is an example in which a vinyl toluene-rich fraction and a rosin glycerin ester are polymerized without using nitrogen, and Example 9 is a reaction procedure different from that in Example 2 in which a vinyl toluene-rich fraction and a rosin glycerin ester are used. This is an example in which is polymerized.

Further, among the production comparative examples 1 to 7, the comparative example 1
Is an example in which only the above-mentioned ordinary C ₉ petroleum resin is used as a tackifier resin, Comparative Example 2 is an example in which only the above-mentioned rosin glycerin ester is similarly used, and Comparative Examples 3 and 4 are both based on the prior art 1 described above. Comparative Example 5 is an example in which a C ₉ petroleum resin and a rosin glycerin ester are simply mixed, and Comparative Example 5 is an example in which a C ₉ petroleum fraction and a rosin are polymerized in accordance with the aforementioned prior arts 2 to 5. Comparative Example 6 is an example in which a rosin ester and a conjugated diene are polymerized in accordance with the above-mentioned prior art 6.

(1) Example 1 100 equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube
After filling 300 parts of trimethylbenzene in a 0 ml four-necked flask, 60 parts of the rosin glycerin ester of Production Example 1 was dissolved in a nitrogen atmosphere while heating to 50 ° C., and trifluoride was used as a Friedel-Crafts catalyst. 1.65 parts of the boron phenol complex were added. Next, 300 parts of a C ₉ petroleum fraction whose monomer amount was adjusted to 50% with trimethylbenzene was dropped into the flask at a rate of 100 parts / hour and added to the rosin ester solution in a stirred state. After completion of the dropwise addition, the mixture was allowed to react for 1 hour at 50 ° C. for aging. Next, an appropriate amount of an alkali was added to neutralize the acid catalyst, and after filtration and removal, the reaction product was heated to 220 ° C. and distilled under reduced pressure to remove the solvent and the unreacted unsaturated petroleum fraction. The desired tackifier resin was obtained.

(2) Example 2 The procedure was based on Example 1 except that the vinyl toluene-rich fraction of the above-mentioned production example was used instead of the C ₉ petroleum fraction and the amount of monomer was adjusted to 50%. The reaction was carried out under the same conditions as in Example 1 to obtain a tackifier resin.

(3) Example 3 Based on Example 1 described above, 240 parts of a C ₉ petroleum fraction having a monomer amount of 50% and 60 parts of ethylidene norbornene having a monomer amount of 50% also adjusted with trimethylbenzene. The mixture was allowed to react under the same conditions as in Example 1 except that the mixture was dropped into the flask to obtain a tackifier resin.

[0054] (4) Example 4 which was the above Example 3 as a basic, except for using the vinyl toluene rich fraction Preparation Example in place of the C ₉ petroleum fraction, as in Example 3 To obtain a tackifier resin.

(5) Example 5 The reaction was carried out under the same conditions as in Example 4 except that 30 parts of dicyclopentadiene was used in place of ethylidene norbornene. Agent resin was obtained.

(6) Example 6 The procedure of Example 2 was repeated except that 60 parts of the maleic anhydride-modified rosin glycerin ester obtained in Production Example 2 was used instead of the rosin glycerin ester. The reaction was carried out under the same conditions as in Example 2 to obtain a tackifier resin.

(7) Example 7 This example was based on Production Example 2 except that the rosin glycerin ester was replaced with the rosin obtained in Production Example 3 and 60 parts of a polymerized rosin glycerin ester. The reaction was carried out under the same conditions as in Example 2 to obtain a tackifier resin.

(8) Example 8 A tackifier resin was obtained under the same conditions as in Example 2 except that polymerization was carried out without using nitrogen, based on Production Example 2 described above.

(9) Example 9 A 100 equipped with a stirrer, thermometer, nitrogen inlet tube and cooling tube
After filling a 0 ml four-necked flask with 300 parts of trimethylbenzene, 1.65 parts of a boron trifluoride phenol complex was added as a Friedel craft catalyst. Next, 60 parts of rosin glycerin ester was dissolved in 300 parts of the vinyltoluene-rich fraction of the above-mentioned preparation example in which the monomer amount was adjusted to 50% with trimethylbenzene, and the solution was dropped into the flask at a speed of 120 parts / hour. It was added to the stirred solvent. After completion of the dropwise addition, the mixture was reacted at 50 ° C. for 1 hour and aged. Next, an appropriate amount of an alkali was added to neutralize the acid catalyst, and after filtration and removal, the reaction product was heated to 220 ° C. and distilled under reduced pressure to remove the solvent and the unreacted unsaturated petroleum fraction. A tackifier resin was obtained.

(10) Comparative Example 1 A commercially available C ₉ petroleum resin (Neopolymer S, manufactured by Nippon Petrochemical Co., softening point: 95 ° C.) was directly used as a tackifier resin.

(11) Comparative Example 2 Commercially available rosin glycerin ester (Hariester DS-
90, manufactured by Harima Chemicals, Inc., softening point 93 ° C.) was used as it was as a tackifier resin.

(12) Comparative Example 3 According to Prior Art 1, without reacting the above C ₉ petroleum resin with rosin glycerin ester, C ₉ petroleum resin / rosin glycerin ester = 10/5 parts by weight It was used as a tackifier resin by mixing as it was in the ratio.

[0063] (13) as in Comparative Example 4 Comparative Example 3 is obtained by using a mixture of C ₉ petroleum resin and rosin glycerin ester tackifier resins, C ₉ petroleum resin / rosin glycerin ester = 7.5 / 7.5 by weight.

(14) Comparative Example 5 This is a tackifier resin obtained by polymerizing a C ₉ petroleum fraction and rosins used in the above Examples, according to Conventional Techniques 2 to 5. That is, a tackifier resin was obtained under the same conditions as in Example 2 except that 60 parts of WW grade tall oil rosin was used instead of the rosin ester based on Example 2 described above.

(15) Comparative Example 6 A tackifier resin obtained by polymerizing a rosin ester and a conjugated diene in accordance with the prior art 6. That is, based on Example 2, under the same conditions as Example 2, instead of the vinyl toluene-rich fraction, 300 parts of isoprene whose monomer amount was adjusted to 50% with trimethylbenzene was added at 100 parts / hour. It was dropped into the flask at a speed and added to the rosin ester solution in a stirring state. After the completion of the dropwise addition, the mixture was reacted at 30 ° C. for 2 hours, and then heated to 50 ° C. and kept for 1 hour for aging. Then, an appropriate amount of alkali is added to neutralize the acid catalyst, and the mixture is filtered and removed. Then, the reaction product is heated to 220 ° C. and distilled under reduced pressure to remove the solvent and unreacted isoprene. A resin was obtained.

<< Example of Property Test of Tackifier Resin >>
The constant number and the polymerization rate of each tackifier resin obtained in Examples 1 to 9 and Comparative Examples 5 to 6 were measured, and are summarized in FIG. The polymerization rate and shows a C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A) and the rosin ester (B), or cyclic diolefins (C) and the reaction rate in the copolymerization. Basically, rosin acids of the abietic acid type (abietic acid, neoabietic acid, parastolic acid) have a conjugated double bond in the molecule, and aromatic unsaturated hydrocarbons (A ) Is presumed to be copolymerized with the above. Therefore, if the consumption of abietic acid type rosin acid in the tackifier resin is measured, the polymerization rate can be derived from the consumption. For this reason, the analysis of the polymerization rate was performed by measuring the amount of abietic acid type rosin acid in the rosin component consumed by the copolymerization. Specifically, rosin acid can be separated from the rosin ester contained in the polymer by hydrolyzing each tackifier resin of Examples and Comparative Examples with an alkali, so that the amount of rosin acid of this abietic acid type is reduced. The polymerization rate (%) was calculated from the following equation by measuring with gas chromatography. Polymerization ratio (%) = {(PQ) / P} × 100 P: Abietic acid amount in raw material rosin ester Q: Abietic acid amount in tackifier resin

According to FIG. 1, first, in comparison of Examples 2, 6, and 7 with Comparative Example 5, when rosin esters were used, the polymerization rate and the number of colors were superior to those of rosins. Turned out to be. As described above, the carboxyl group of the rosin, or reduce the rate of polymerization act as a catalyst poison the polymerization catalyst BF _3, but itself decarboxylated may induce decomposition of the rosin, use a rosin ester In Examples 2, 6, and 7, which had been described above, these adverse effects were avoided.
It is thought that this promoted the lightening of the tackifier resin and the polymerization rate, and revealed the remarkable superiority of polymerizing rosin esters instead of rosins. Example 2
Comparing 4 to 7 with Examples 1 and 3, the tackifier resin produced with a vinyl toluene-rich fraction has a higher yield than the resin produced with a normal C ₉ petroleum fraction that has not been precision distilled.
The number of colors became light in three stages. It is considered that the number of colors of the polymer was significantly reduced by removing impurities causing coloring, for example, coloring conjugated diolefins, nitrogen compounds, sulfur compounds and the like in the precision distillation stage. Further, when Examples 2 and 8 are compared, when the reaction is performed in a nitrogen atmosphere, the number of colors of the tackifier resin becomes four steps lighter and the copolymerization ratio is 14% as compared with the case where nitrogen is not used. It was higher. Again, as described above, when reacting in air, the polymer or raw material is oxidized and colored, or oxygen acts as a reaction inhibitor to reduce reactivity, but by reacting in a nitrogen atmosphere, these It seems that the adverse effects were avoided. On the other hand, in contrast to the case where the type of rosin ester was changed, in Example 6 using glycerin ester of maleic anhydride-modified rosin and Example 7 using glycerin ester of rosin and polymerized rosin,
The softening point of the tackifier resin was higher by about 20 ° C. than in Example 2 using rosin glycerin ester. Therefore, it was found that by controlling the softening point of the rosin ester to be used, the softening point of the tackifier resin can be adjusted to a desired value. On the other hand, when Examples 2 and 9 having different reaction procedures are compared with each other, Example 2 in which a vinyltoluene-rich fraction was later added to a solvent in which a rosin ester and a catalyst were previously dissolved was compared with a vinyltoluene-rich fraction. From Example 9 in which rosin esters were simultaneously added to the solvent, it was found that the conversion was high. In general, rosin ester has a low reactivity, because the C ₉ petroleum fraction has tendency to make a homopolymer because of high reactivity, addition of petroleum fraction to contain rosin esters catalytic Thus, it is considered that the production of a homopolymer of the petroleum fraction was suppressed, and the polymerization rate was increased.

<< Production Example of Solvent-Type Acrylic Pressure-Sensitive Adhesive >>
Accordingly, a pressure-sensitive adhesive was prepared by adding each tackifier resin of the above Production Examples 1 to 9 and Comparative Examples 1 to 6 to an acrylic polymer, and as described below, the SU of the pressure-sensitive adhesive in a normal state was prepared.
Adhesion performance evaluation tests for S, polyethylene, polypropylene, glass, adhesion holding power for SUS, and tackiness were performed.

That is, 800 parts of n-butyl acrylate and 2-ethylhexyl acrylate as monomer components for polymerization were placed in a 3 L glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube. Parts, 40 parts of acrylic acid,
600 parts of toluene and 600 parts of ethyl acetate were charged as a solvent, and 3 parts of benzoyl peroxide was further added as a polymerization initiator, followed by stirring while blowing in nitrogen gas.
After replacing the air in the system with nitrogen, the system was heated to a temperature of 75 ° C. The polymerization reaction was performed at 75 ° C. for 8 hours to obtain a solution of an acrylic copolymer. The nonvolatile content of this acrylic copolymer solution was 45.9%, and the viscosity was 9300 mPa · s / 25.
° C. Next, the acrylic copolymer solution 10
15 parts of each tackifier resin of Examples 1 to 9 and Comparative Examples 1 to 6 with respect to 0 parts, and 45% of an adduct of tolylene diisocyanate and trimethylolpropane as a curing agent
A solvent-type acrylic pressure-sensitive adhesive was produced by adding 1 part of an ethyl acetate solution. A pressure-sensitive adhesive prepared with only the above acrylic copolymer solution without adding a tackifier resin was used as Comparative Example 7.

<< Example of Evaluation Test of Adhesive Performance of Pressure-Sensitive Adhesive >> Then, a solution of each of the pressure-sensitive adhesives of Examples 1 to 9 and Comparative Examples 1 to 7 was applied to a 25 μm-thick polyester film (Lumirror film: Toray Industries, Inc.). Manufactured), the thickness of the coating film after drying is 4
The film was coated with an applicator so as to have a thickness of 0 μm, and dried with a hot air drier at 80 ° C. for 3 minutes to obtain a pressure-sensitive adhesive performance evaluation film, which was used as a test piece. Next, from the viewpoint of accelerating the reaction between the base polymer and the curing agent, the test piece was stored in a thermo-hygrostat at a temperature of 25 ° C. and a relative humidity of 65% for 7 days and subjected to a performance evaluation test.

Various performance evaluation methods are as follows. (1) Adhesion Strength In accordance with JISZ-0237 and Z-1528, using a stainless steel plate (one obtained by polishing and polishing SUS304 with 280-size abrasive paper), polyethylene, polypropylene, and a glass plate as adherends The peel strength (unit: gf / 25 mm) when peeled at a rate of 300 mm / min in the 180 ° direction was measured. The measurement atmosphere was set to a normal state at a temperature of 23 ° C. and a relative humidity of 50%.

(2) Adhesive Retention Force A stainless steel plate (a surface of SUS304 polished with 280 size abrasive paper and surface processed) was used as an adherend in accordance with JIS Z-0237 and Z-1528. ×
The above test piece of 25 mm was adhered, and the width of displacement (cm) after applying a load for 1 hour at each of 40 ° C., 60 ° C., and 80 ° C. while applying a load of 1 kg in the direction of gravity was measured.

(3) Tackability In accordance with JIS Z-0237 and Z-1528, each of the above test pieces was fixed on a slope having an inclination angle of 30 degrees, and 1/32 (steel ball No. 1) to 32/32 (Steel ball No. 32)
The number of the largest steel ball rolling an inch steel ball and stopping on the adhesive surface was measured in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. In this test, it can be determined that the larger the steel ball number is, the better the constant temperature property is.

FIG. 2 to FIG. 3 show the test results. C ₈ ~
A copolymer of a C ₁₀ aromatic unsaturated hydrocarbon (hereinafter referred to as a C ₉ petroleum fraction) and a rosin ester, or a copolymer of a predetermined cyclic diolefin and a tackifier resin. In Examples 1 to 9, it was found that there was no deviation in the adhesive strength, tackiness, and holding power, and that all exhibited excellent balanced adhesive properties. On the other hand, in Comparative Example 1 containing only C ₉ petroleum resin, the adhesive holding power was good, but the adhesive strength and tackiness were inferior. Conversely, in Comparative Example 2 containing only rosin esters, The adhesive strength and tackiness were good, but the adhesive holding power was poor. In addition, the above-mentioned prior art 2
In Comparative Example 3-4 were simply mixed C ₉ petroleum resin and rosin ester in conformity with a low adhesive holding power and tackiness at high temperature, adhesive force, tackiness, bias was observed in the adhesive holding power Was. In Comparative Example 5 in which the C ₉ petroleum fraction and the rosin were polymerized, the adhesive strength (particularly the adhesive strength to polyolefin) and the adhesive holding power were inferior. The force and adhesive holding power were low.

A more detailed analysis of the case where the tackifier resins of Examples 1 to 9 were used revealed that Examples 3 to 4 in which cyclic diolefins having no polar group such as ethylidene norbornene and dicyclopentadiene were polymerized as the third component. In No. 5, it became clear that the adhesive strength to polyethylene and polypropylene was remarkably increased as compared with the other examples having no third component. Incidentally, the adhesive strength was at a level not seen in Comparative Examples 1 to 7. Also,
Example Polymerization was conducted in a nitrogen atmosphere, or, in a solvent dissolving the rosin ester and a catalyst, later C ₉ petroleum fractions, or in yet embodiment the addition of cyclic diolefins, it As compared with the examples other than the above, the adhesive holding power at high temperature and the tackiness tended to be improved. From the above,
The tackifier resin of the present invention obtained by polymerizing a C ₉ petroleum fraction and a rosin ester, and further a cyclic diolefin,
It has been found that they exhibit well-balanced and excellent adhesive properties not found in applications where only existing tackifier resins are mixed or tackifier resins according to the prior art mentioned above.

[Brief description of the drawings]

FIG. 1 is a table showing properties test results of each tackifier resin of Examples 1 to 9 and Comparative Examples 5 to 6.

FIG. 2 is a table showing test results of the adhesive strength of acrylic pressure-sensitive adhesives using or not using each tackifier resin of Examples 1 to 9 and Comparative Examples 1 to 7.

FIG. 3 is a table showing test results of tackiness and tackiness of acrylic pressure-sensitive adhesives using or not using each tackifier resin of Examples 1 to 9 and Comparative Examples 1 to 7. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09J 201/00 C09J 201/00 F term (Reference) 4J040 BA201 BA202 CA011 CA081 CA151 DA051 DB051 DF031 DK021 DK022 DM011 DN031 DN032 EF001 JB09 KA26 LA06 QA01 4J100 AR15R AR17R AR22R AS15R AU03P AU10R AU16Q AU21R CA04 CA05 JA03

Claims (10)

[Claims] 1. An adhesive obtained by polymerizing (A) a C ₈ -C ₁₀ aromatic unsaturated hydrocarbon, and (B) a rosin ester obtained by esterifying at least one of a rosin and a rosin derivative with an alcohol. Granting agent resin. 2. (A) C ₈ -C ₁₀ aromatic unsaturated hydrocarbons, (B) rosin esters obtained by esterifying at least one of rosins and rosin derivatives with alcohols, and (C) a polar group A tackifier resin obtained by polymerizing cyclic diolefins having no tackifier. 3. The cyclic diolefin (C) is ethylidene norbornene, ethylidene bicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene,
The tackifier resin according to claim 2, which is limonene, dipentene, or the like. 4. The tackifier resin according to claim 1, wherein the alcohol is a dihydric to tetrahydric alcohol. 5. The C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A)
But claim 1, wherein the distilled to obtain purified C ₉ petroleum fractions, vinyltoluene content in all monomers is a vinyl toluene-rich fraction is 40 to 80 wt% The tackifier resin according to any one of the above. 6. C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A)
And a rosin ester (B) obtained by esterifying at least one of a rosin and a rosin derivative with an alcohol to produce a tackifier resin, wherein (A) / (B) = 30 to 95% by weight % / 70 to 5% by weight, a method for producing a tackifier resin. 7. C ₈ -C ₁₀ aromatic unsaturated hydrocarbons (A)
And a method for producing a tackifier resin by polymerizing a rosin ester (B) obtained by esterifying at least one of a rosin and a rosin derivative with an alcohol, and a cyclic diolefin having no polar group (C). A method for producing a tackifier resin, comprising polymerizing the cyclic diolefin (C) at a ratio of 1 to 50% by weight. 8. A nitrogen atmosphere comprising adding an aromatic unsaturated hydrocarbon (A) and a rosin ester (B), or further adding a cyclic diolefin (C) to the (A) and (B). 8. The method for producing a tackifier resin according to claim 6, wherein the polymerization is carried out under the following conditions. 9. Polymerization by adding an aromatic unsaturated hydrocarbon (A) or further adding a cyclic diolefin (C) to a solvent in which a rosin ester (B) and an acid catalyst are dissolved. The method for producing a tackifier resin according to any one of claims 6 to 8, wherein the reaction is performed. 10. An acrylic, natural rubber, SBR,
An adhesive composition characterized by adding the tackifier resin according to any one of claims 1 to 5 to a base polymer such as SIS, EVA, urethane, and CR.