JP2001031882A - Organic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting excellent flexibility, low stress properties, adhesion, tackiness, etc., by including a polymer and an isocyanate-terminated isobutylene-based polymer as essential components. SOLUTION: This composition comprises (A) a polymer (preferably a thermosetting resin, a thermoplastic resin, a thermoplastic elastomer or a rubber), (B) a hydroxyl group-terminated isobutylene-based polymer and/or an isocyanate- terminated isobutylene-based polymer obtained by reacting the hydroxyl group- terminated isobutylene-based polymer with a polyisocyanate compound as essential components (with the proviso that the component B is not included in the component A). The component B in an amount of preferably 0.1-100 pts.wt., more preferably 1-50 pts.wt. based on 100 pts.wt. of the component A is contained. The objective composition can be prepared by including 1-50 pts.wt. of the component B, (C) 10-150 pts.wt. of a tackifier and (D) 10-150 pts.wt. of a plasticizer in 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polymer composition obtained by imparting a new function to a polymer compound and improving its properties.

[0002]

2. Description of the Related Art Polymer materials are used in many fields, but are generally rarely used alone, and are used as compositions containing various additives.

[0003] For example, epoxy resins known as thermosetting resins also generally have the property of being hard and brittle, and have the disadvantage that cracks occur due to stress distortion and thermal shock during curing or use. It is desired to make the epoxy resin tough, impart flexibility and rubber elasticity, and reduce stress. It is also known to add a modifier for the purpose of improving the adhesion such as adhesion and coating.

[0004] Polycarbonate resin, which is a thermoplastic resin, is excellent in mechanical strength such as tensile strength, bending strength and impact strength, heat resistance, etc., but is required to improve low temperature impact resistance, solvent resistance, fluidity and the like. A resin composition in which a hydrogenated (styrene-isoprene-styrene) block copolymer is blended (Japanese Patent Application Laid-Open No. 58-145557), a resin composition in which an acrylic rubber is blended (Japanese Patent Publication No. 43-18611, JP-B-48-29308, JP-A-53-34153, JP-A-56-143329, etc.) have been proposed.

[0005] Further, polyolefin resins which are thermoplastic resins are used in many industrial fields. However, it is known that a polyolefin resin has a problem in paintability and the like unless modified.In practice, modification is performed by adding a hydrogenated polydiene polyol or the like to improve this problem. (Examined Japanese Patent Publication No. 53-316)
62 etc.).

As a main use of the thermoplastic elastomer, for example, a hydrogenated (styrene-isoprene-styrene) block copolymer is used as a pressure-sensitive adhesive. An imparting agent and the like are added (JP-A-10-212390, etc.).

[0007] Further, for rubber materials, for example, rubber rolls used in electronic copying machines and the like are required to have low hardness, and methods such as addition of a plasticizer have been adopted (Japanese Patent Application Laid-Open No. 11-911178). .

[0008]

Non-reactive organic rubbers or thermoplastic elastomers are often used as additives for modifying polymer compounds.
Conventional materials contain unsaturated bonds, ether bonds, ester bonds, and the like in the polymer main chain skeleton, and have problems in terms of weather resistance and chemical resistance.

[0009]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that (B) a hydroxyl-terminated isobutylene-based polymer and / or a hydroxyl-terminated isobutylene-based polymer having excellent weather resistance and chemical resistance. By adding an isocyanate-terminated isobutylene-based polymer obtained by the reaction between the polymer and the polyisocyanate compound to the polymer (A) (excluding the polymer of the component (B)), the polymer becomes flexible. Have been found to be able to impart properties, low stress, adhesion, tackiness, heat resistance, weather resistance, chemical resistance, low gas permeability, low moisture permeability, high vibration absorption, etc., and complete the present invention. Reached.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to (A) a polymer compound (excluding the polymer of the component (B)), (B) a hydroxyl-terminated isobutylene-based polymer and / or a hydroxyl-terminated isobutylene-based polymer. The present invention relates to a composition containing, as an essential component, an isocyanate-terminated isobutylene-based polymer obtained by a reaction with an isocyanate compound.

The isobutylene polymer which is a component that characterizes the present invention is known as a compound having properties such as heat resistance, weather resistance, chemical resistance, low gas permeability, low moisture permeability, and high vibration absorption. An isobutylene-based polymer having a reactive group introduced at a terminal can impart these properties to a polymer material, and furthermore, it is possible to carry out a cross-linking reaction using a terminal functional group. By doing so, it becomes a rubber-like component, so that it is possible to impart flexibility to the composition and to alleviate stress inside the resin.

The polymer compound used in the present invention is not particularly limited, but the polymer compound may be one or more components selected from the group consisting of a thermosetting resin, a thermoplastic resin, a thermoplastic elastomer, and a rubber. Preferably, the composition comprises:

[0013] Since a polymer compound is modified by adding a hydroxyl-terminated isobutylene polymer and / or an isocyanate-terminated isobutylene polymer obtained by reacting a hydroxyl-terminated isobutylene polymer with a polyisocyanate compound, The addition ratio is as follows: (B) a hydroxyl-terminated isobutylene-based polymer and / or a hydroxyl-terminated isobutylene-based polymer and a polyisocyanate compound per 100 parts by weight of the polymer compound (A) (excluding the polymer of the component (B)). Is preferably added in the range of 0.1 to 100 parts by weight, more preferably in the range of 1 to 50 parts by weight.

Further, in the case where the polymer compound (A) (excluding the polymer of the component (B)) is a thermoplastic elastomer, (B) a hydroxyl group-terminated isobutylene-based polymer is used per 100 parts by weight of the component (A). 1 to 50 parts by weight of the isocyanate-terminated isobutylene-based polymer obtained by the reaction of the unionized and / or hydroxyl-terminated isobutylene-based polymer with the polyisocyanate compound, and 10 to 15 parts by weight of the (C) tackifier.
By using 0 parts by weight and 10 to 150 parts by weight of the plasticizer (D), compared to the pressure-sensitive adhesive composed of the components (A), (C) and (D) (that is, one containing no component (B)) A tacky composition with further improved adhesiveness can be obtained.

The (B) hydroxyl-terminated isobutylene-based polymer and / or the isocyanate-terminated isobutylene-based polymer obtained by reacting the hydroxyl-terminated isobutylene-based polymer with a polyisocyanate compound according to the present invention is a component which is a feature of the present invention. is there.

The number of hydroxyl groups in one molecule of the (B) hydroxyl-terminated isobutylene polymer of the present invention is usually one or more.
It is preferable that there are 1 to 5. When the number of hydroxyl groups in one molecule is less than one, it becomes difficult to form an elastomer by a curing reaction in the composition of the isobutylene-based polymer, and it becomes difficult to develop sufficient strength, or bleeding from resin occurs. It is concerned. Further, the effect of modifying the surface of the composition by the polar group may be reduced.

When the hydroxyl group is located at the terminal of the molecular chain of the isobutylene polymer, the amount of the effective network chain of the isobutylene polymer component contained in the finally formed cured film increases, so that a high-strength film is formed. The hydroxyl group is preferably at the terminal, since it is easy to obtain.

The molecular weight of the isobutylene-based polymer used in the present invention is not particularly limited, but is preferably from 1,000 to 100,000 from the viewpoint of moldability and various properties.
More preferably, it is 3000 to 20,000.

The isobutylene polymer having a hydroxyl group at the terminal according to the present invention is not particularly limited, but can be produced, for example, by the following method. J. P. Kenne
dy et al. first synthesize a polyisobutylene having a chlorine group at the terminal synthesized by living cationic polymerization, and then perform a dehydrochlorination reaction of the terminal with ^t BuOK to lead to an isopropenyl group terminal group, or after synthesizing the polyisobutylene allyl group-terminated by reaction with allyltrimethylsilane under titanium chloride present, a hydride such as BH ₃ or 9-BBN -
It discloses a method for quantitatively introducing a hydroxyl group to a terminal by using a borane reagent and hydrogen peroxide (for example, B.
Ivan, JP Kennedy, and VSC Chang, J. Pol
ym. Sci., Polym. Chem, Ed., 1980, 18, 3177 and B. Ivan, and JP Kennedy, Polym. Mater. Sc.
i. Eng., 1988, 58, 866, etc.).

The hydroxyl group-terminated isobutylene polymer according to the present invention comprises a halogen-terminated isobutylene polymer obtained by cationic polymerization forming a carbon-carbon single bond, a protected hydroxyl group and a carbon-carbon double bond. Can be also obtained by producing an isobutylene-based polymer having a protected hydroxyl group at the terminal by a reaction with a compound having the following formula, and then deprotecting the hydroxyl group.

The isobutylene-based polymer having a protected hydroxyl group at the terminal is represented by the following formula: R ¹ (AX) _a (1) (wherein R ¹ is a monovalent compound having a single ring or a plurality of aromatic rings, X is a chlorine or bromine group, a is an integer of 1 to 4. A is a polymer of one or more cationic polymerizable monomers, and the polymerizable monomer is at least An isobutylene as an essential component. When a is 2 or more, A may be the same or different.) And a halogen-terminated isobutylene-based polymer obtained by cationic polymerization, and a compound represented by the formula 2: CH ₂ ＣC (R ² ) -B-OG (2) (wherein, R ² is hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, B is a divalent hydrocarbon group having 1 to 30 carbon atoms, and G is Represents a protecting group for a hydroxyl group). That.

In the formula (2), B represents 1 to 30 carbon atoms.
A divalent hydrocarbon group having 0 to 5 carbon-carbon double bonds (excluding those having a CH ₂ ＣC (R ² ) -group (R ² is the same as described above)) and / or Alternatively, it is preferable to have 0 to 3 aromatic rings. B in the equation (2) is 0
It is more preferred to have up to three divalent groups represented by -CH = CH-.

The compound of the formula (2) includes a compound of the formula (3): CH ₂ ＣC (R ² )-(CH ₂ ) _b -｛-CH ＝ CH- (C
H ₂ ) _c ｝ _n -OG (3) (wherein, R ² represents hydrogen or a saturated or unsaturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and b and c are integers of 1 to 30) And n may be the same or different, and n is an integer of 0 to 5, and G represents a hydroxyl-protecting group.)

The isobutylene polymer having a protected hydroxyl group at the terminal obtained by this method can be easily converted to an isobutylene polymer having a hydroxyl group at the terminal by deprotection.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having a copolymer with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good.

Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes and the like. Examples of such a copolymer component include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane,
Vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinyl Methylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallylmethoxymethoxy, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ
-Methacryloyloxypropylmethyldimethoxysilane.

The protecting group of the compound containing a protected hydroxyl group and a carbon-carbon double bond is not particularly limited as long as it provides a hydroxyl group by deprotection.
It is an inorganic or organic group having 0 to 54 carbon atoms. Preferred protecting groups that can be deprotected under mild conditions include the following.

[0028]

Embedded image (Wherein, R ³ , R ⁴ , and R ⁵ are hydrogen or C 1 to C 1)
8 represents a saturated or unsaturated hydrocarbon group, and the groups containing a plurality of Rs may be the same or different. X
Is a functional group selected from Cl, Br and I. M ¹ is L
a monovalent metal selected from i, Na and K, M ² is Mg, C
a, a divalent metal selected from Sr and Ba, M ³ is B or A
1, a trivalent metal selected from Ga, M ⁴ is Ti, Zr,
It is a tetravalent metal selected from Hf, Si, Ge, Sn, and Pb. Examples of the protecting group include an alkyl group, an acyl group, and an RC (O) — group (where R is 1 to 10 carbon atoms) in view of availability, ease of separation of the polymer and the protecting group component after deprotection. Preferred are a saturated hydrocarbon group), a silyl group and a metal alkoxide, and a methyl group, an ethyl group, n- and i-propyl groups, and n
-, I- and t-butyl, formyl, acetyl,
Propionyl group, butyryl group, benzoyl group, trimethylsilyl group, triphenylsilyl group is more preferable,
It is particularly preferred that these protecting groups have from 0 to 54 carbon atoms.

The compound having a protected hydroxyl group and a carbon-carbon double bond represented by the above formula (2), which is a substrate to be reacted with the halogen-terminated isobutylene polymer represented by the above formula (1) includes: 1 substitution or 1,
Although it is not particularly limited as long as it is an olefin having a hydroxyl group protected at the terminal of 1′-2 substitution, when G is hydrogen in the above formula (2),
Allyl alcohol, methallyl alcohol, 3-butene
1-ol, 3-methyl-3-buten-1-ol, 4
-Penten-1-ol, 5-hexen-1-ol,
6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol and 10-undecene-1-ol, 2,5-hexadienol, 2, 6-heptadienol, 3,6-heptadienol, 2,7-octadienol, 3,7-octadienol, 4,7-octadienol, 2,8-
Nonadienol, 3,8-nonadienol, 4,8-nonadienol, 5,8-nonadienol, 2,9-decadienol, 3,9-decadienol, 4,9-decadienol, 5,9-decadienol or 6,9-decadienol The selected compound is preferred.

The halogen-terminated isobutylene polymer obtained by the cationic polymerization of the above formula (1) is added to the above formula (2)
When reacting a compound containing a protected hydroxyl group and an element-carbon double bond represented by the following formula, a Lewis acid can be used as a catalyst. In this case, there is no particular limitation as long as it is a Lewis acid, but TiCl ₄ , AlCl ₃ , BC
It is preferable because the reaction activity of l ₃ and SnCl ₄ is high and the selectivity is good.

In the present invention, it is possible to use a single or a mixed solvent arbitrarily selected from halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons as the reaction solvent. Must be at least one component selected from methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, and n-butyl chloride as halogenated hydrocarbons in terms of solubility and reactivity. Is preferred. For the same reason, the aromatic hydrocarbon is preferably toluene, and the aliphatic hydrocarbon is pentane, n-hexane,
One or more components selected from cyclohexane, methylcyclohexane and ethylcyclohexane are preferred.

As a reaction solvent which does not use halogenated hydrocarbons, which may be adversely affected on the environment, for example, toluene, ethylcyclohexane, or a mixed solvent thereof is used to obtain an isobutylene-based polymer having a protected hydroxyl group at its terminal. Can be easily achieved.

The deprotection reaction is not particularly limited as long as it is a reaction for introducing a protecting group into a hydroxyl group. Preferred reactions include a hydrolysis reaction and a thermal decomposition reaction.

The hydrolysis reaction can be carried out in either a solvent system or a non-solvent system. The solvent used for the solvent-based reaction is not particularly limited, but it is preferable to use a solvent for producing an isobutylene-based polymer having a protected hydroxyl group at the terminal. The conditions for performing the hydrolysis may be either acidic or basic conditions, but it is preferable to perform the hydrolysis reaction using a basic aqueous solution in view of the efficiency of the hydrolysis reaction.

The reagent used in the hydrolysis under basic conditions is not particularly limited as long as it is an organic or inorganic basic compound used in a usual hydrolysis reaction. , Potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium acetate, potassium acetate, lithium acetate, calcium acetate, magnesium acetate, t-butoxy Particularly preferred are potassium, sodium t-butoxide, potassium methoxide, sodium methoxide and the like.

In the hydrolysis reaction, the reaction can be efficiently advanced by adding a catalyst. As such a catalyst, any of an organic catalyst and an inorganic catalyst can be reacted, but an organic salt is preferable in terms of easiness of the reaction, and a quaternary ammonium salt is particularly preferable. Representative ammonium salts include triethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, N-laurylpyridinium chloride, n-butylammonium, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide. Tetra-n-butylammonium bromide, tetrabutylammonium hydrogen sulfate, N-benzylpicolinium chloride, tetramethylammonium iodide, iodine tetra-n-butylammonium, N-lauryl-4-picolinium chloride, N-lauryl Picolinium chloride and the like.

For example, an isobutylene-based polymer obtained by cationic polymerization in which a polymer main chain having a hydroxyl group at a terminal forms a carbon-carbon single bond is specifically obtained by the following production method. Chloroform, methylene chloride, 1,1- and 1 to 4 equivalents of a halogen-terminated isobutylene-based polymer represented by the formula (1) are reacted with an equivalent of 1 to 4 equivalents of a protected hydroxyl-terminated olefin compound represented by the formula (2). Dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, toluene, pentane, n
-Hexane, cyclohexane, methylcyclohexane,
It is dissolved in a solvent consisting of one or more components selected from ethylcyclohexane. Then, in the presence of an electron donor such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-di-t-butylpyridine, etc., at a temperature range of -100 ° C to -30 ° C, Ti
By adding a Lewis acid catalyst such as Cl ₄ , AlCl ₃ , BCl ₃ , SnCl _{4 and} reacting for 30 minutes to 5 hours, an isobutylene-based polymer having a protected hydroxyl group at the terminal can be obtained. By deprotecting this, an isobutylene-based polymer having a hydroxyl group at a terminal can be obtained.

In the composition of the present invention, the hydroxyl-terminated isobutylene-based polymer may be used as it is, or an isocyanate-terminated isobutylene-based polymer obtained by reacting it with a polyisocyanate compound may be used. It is also effective to use a mixture of a hydroxyl group-terminated isobutylene polymer and a polyisocyanate compound.

The polyisocyanate compound which can be used is not particularly limited, but the main polyisocyanate compounds include methylene diphenyl diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene 1, 5-diisocyanate and tetramethyl xylene. Examples include diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, trimethylhexamethylene diisocyanate, norbornene diisocyanate, and the like.

The isocyanate-terminated isobutylene polymer can be prepared by a usual reaction method of a hydroxyl group-containing compound and an isocyanate compound, and can be obtained by reacting either a solvent system or a non-solvent system. Usually, a reaction in a solventless system that does not require solvent removal is preferred. 0 ° C-18
The isocyanate-terminated isobutylene-based polymer can be obtained by reacting in a temperature range of 0 ° C. for 30 minutes to 6 hours, but a catalyst may be used to accelerate the reaction. Examples of the catalyst used include dimethoxydibutyltin, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetylacetonate, and tin octylate.

The above-mentioned hydroxyl-terminated isobutylene-based polymer and / or the isocyanate-terminated isobutylene-based polymer obtained by reacting the hydroxyl-terminated isobutylene-based polymer with a polyisocyanate compound may have high viscosity and poor workability. . In that case, various plasticizers may be added to the extent that the adhesiveness and stainability of the composition are not deteriorated for the purpose of lowering the viscosity of the polymer and improving handling.

A plasticizer having good compatibility with the hydroxyl-terminated isobutylene polymer and / or the isocyanate-terminated isobutylene polymer obtained by reacting the hydroxyl-terminated isobutylene polymer and the polyisocyanate compound as the component (B) of the present invention. Examples thereof include polyvinyl oligomers such as polybutene, hydrogenated polybutene, hydrogenated α-olefin oligomer and atactic polypropylene; aromatic oligomers such as biphenyl and triphenyl; hydrogenated polyene such as hydrogenated liquid polybutadiene Oligomers; paraffinic oligomers such as paraffin oil and chlorinated paraffin oil; cycloparaffinic oligomers such as naphthenic oil.

Further, a phthalate ester plasticizer, a non-aromatic dibasic ester ester plasticizer, a phosphate ester plasticizer, etc., to such an extent that the adhesiveness, weather resistance and heat resistance of the composition of the present invention are not reduced. Alternatively, it may be used in combination with the above plasticizer. These may be used alone or in combination of two or more.

The above-mentioned plasticizer may be used in place of the solvent for the purpose of adjusting the reaction temperature and adjusting the viscosity of the reaction system when introducing an isocyanate group into the hydroxyl group-terminated isobutylene-based polymer.

The blending amount of the plasticizer is 100 parts by weight of a hydroxyl group-terminated isobutylene-based polymer and / or an isocyanate-terminated isobutylene-based polymer obtained by reacting a hydroxyl group-terminated isobutylene-based polymer with a polyisocyanate compound. )) Is preferably 0.1 to 150 parts.

As the polymer compound as the component (A) of the present invention, any compound having a molecular weight of 1,000 or more can be used without particular limitation. Preferred polymer compounds include thermosetting resins, thermoplastic resins, thermoplastic elastomers, rubbers, and the like. These may be used alone or in combination of two or more (for example, a mixture of a thermosetting resin and a thermoplastic resin may be used).

The thermosetting resin of the present invention is not particularly limited, but specific examples thereof include phenol resin, polyurethane resin, melamine resin, urea resin, epoxy resin, unsaturated polyester, alkyd resin, ebonite and the like. Can be mentioned.

These thermosetting resins can be used alone or as a mixture.

The epoxy resin is not particularly limited, and various types can be used. For example, glycidyl ether type epoxy resins such as bisphenol A, bisphenol F and tetrabromobisphenol A, novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, p -Glycidyl oxybenzoate ether ester type epoxy resin, m-
Aminophenol epoxy resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol Examples include, but are not limited to, glycidyl ethers of polyhydric alcohols such as diglycidyl ether and glycerin, and epoxidized products of unsaturated polymers such as hydantoin type epoxy resins and petroleum resins. These epoxy resins can be used alone or in combination of two or more.

Examples of the thermoplastic resin include an aromatic vinyl compound resin which is a resinous polymer at room temperature.
Representative examples include polystyrene, high impact polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, styrene-maleic anhydride copolymer, and the like.

Examples of other thermoplastic resins include polyolefin resins. Specific examples thereof include homopolymers of α-olefins, random copolymers, block copolymers and mixtures thereof, and α-olefins. Random copolymers with other unsaturated monomers, block copolymers,
Graft copolymers and oxidized, halogenated or sulfonated versions of these polymers, which are at least partially crystalline. Specific examples include polyethylene, polypropylene, polybutene, polymethylpentene, propylene-ethylene copolymer, ethylene-butene-1 copolymer, chlorinated polyethylene, chlorinated polypropylene and the like.

Other thermoplastic resins include polyphenylene ether resins, and specific examples thereof include:
Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, Poly (2,6-dibutyl-1,4-
Phenylene) ether, poly (2,6-diphenyl-)
1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-diphenylene) ether, poly (2,6
-Dichloro-1,4-phenylene) ether, also 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and 2,
3, 5, 6-tetramethylphenol copolymer and the like. Further, those obtained by graft copolymerizing styrene can also be used.

Another thermoplastic resin is a polycarbonate resin, a specific example of which is a thermoplastic branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with a dihydric phenol or a carbonate precursor. .

Here, as the dihydric phenol which can be suitably used, there are bisphenols, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable. Further, 2,2-bis (4-hydroxyphenyl) propane may be partially or entirely replaced with another dihydric phenol. Further, bis (4-hydroxyphenyl) alkanes other than 2,2-bis (4-hydroxyphenyl) propane; hydroquinone; 4,4'-dihydroxydiphenyl; bis (4-hydroxyphenyl) cycloalkane; Phenyl) sulfide; bis (4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) sulfoxide;
Compounds such as hydroxyphenyl) ether or bis (3,5-dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-cyclo-4-hydroxyphenyl) propane, and the like. it can.

Examples of other thermoplastic resins include polyvinyl chloride resin, polyvinyl oxide resin, poly (meth) acrylate resin, poly (meth) acrylamide resin, poly (meth) acrylonitrile resin,
Examples thereof include a polyamide resin, a polyester resin, a polyacetal resin, a polysulfone resin, a polyarylene sulfide resin, a fluorine resin, a polyimide resin, and a thermoplastic polyurethane resin.

Examples of the polyvinyl chloride resin include polyvinyl chloride, polyvinylidene chloride, a polyvinyl chloride-vinylidene chloride copolymer and the like;
Polyvinyl acetate polymer, partially saponified or acetalized polyvinyl acetate polymer; poly (meth) acrylate resins include (meth) acrylic acid such as methyl (meth) acrylate and ethyl (meth) acrylate Ester polymers or copolymers; poly (meth) acrylamide resins such as (meth) acrylamide, alkyl-substituted (meth) acrylamide polymers or copolymers; poly (meth) acrylonitrile resins Poly (meth) acrylonitrile, etc .;
Polycondensates of dicarboxylic acids and diamines, polycondensates of α-aminocarboxylic acids, ring-opening polymers of cyclic lactams, and the like. Specific examples include nylon-46, nylon-6, nylon-66, and nylon. 610, nylon-11, nylon-12, etc .; polyacetal resins such as copolymers of polyoxymethylene, formaldehyde or trioxane with other aldehydes, cyclic ether cyclic carbonates, epoxides, isocyanates, vinyl compounds, etc .; polyesters Examples of the resin include polyethylene terephthalate and polybutylene terephthalate.

Examples of the fluororesin include polytetrafluoroethylene and the like; examples of the polyimide resin include polyimide obtained by reacting an aromatic diamine compound with an aromatic tetracarboxylic dianhydride.

Examples of the thermoplastic polyurethane resin include a thermoplastic polyurethane having a block of a polyol (polyester or polyether) and a diisocyanate as a soft segment and a block of a diisocyanate and a glycol as a hard segment. Specifically, examples of the polyester diol include poly (1,4-butylene adipate), poly (1,6-hexane adipate), and polycaprolactone. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, And polyoxytetramethylene glycol. Further, glycols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Diisocyanates include aromatic, alicyclic, and aliphatic diisocyanates, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

Further, as the thermoplastic resin used in the present invention, various copolymers can be further exemplified. Specific examples of various copolymers include styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-ethyl acrylate copolymer,
Styrene-acrylonitrile-ethyl acrylate copolymer, styrene-ethylene-propylene-acrylonitrile copolymer, styrene-butadiene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, propylene-ethyl acrylate copolymer, Vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride- (meth) acrylate copolymer, vinyl chloride-maleic Acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl acetate-ethylene or propylene copolymer, vinyl acetate-acrylonitrile copolymer, vinyl acetate-acrylic ester Copolymers and the like. .

The thermoplastic elastomer used in the present invention is not particularly limited. Examples of the main compounds include styrene-based elastomers, olefin-based elastomers, PVC-based elastomers, urethane-based elastomers, ester-based elastomers, amide-based elastomers, and others. The thermoplastic elastomer is basically composed of a hard segment and a soft segment. Typical hard segments / soft segments are polystyrene / polybutadiene, polystyrene / polyisoprene, polystyrene / hydrogenated polybutadiene, polystyrene / hydrogenated polyisoprene, and polystyrene. / Polyisobutylene, polystyrene / hydrogenated (styrene) butadiene rubber, polypropylene or polyethylene / hydrogenated (styrene) butadiene rubber, polypropylene and / or polyethylene / ethylene propylene rubber, crystalline polyvinyl chloride / amorphous polyvinyl chloride or acrylonitrile butadiene Rubber, urethane structure / polyester or polyether, polyester / polyester or polyether, polyamide / polyether Stell or polyether, crystalline polyethylene / chlorinated polyethylene, metal carboxylate ion cluster / amorphous polyethylene, syndiotactic-1,2-polybutadiene /
Examples include amorphous polybutadiene, trans-1,4-polyisoprene / amorphous polyisoprene, fluororesin / fluororubber, crystalline polyethylene / EVA or EEA.

The rubber used in the present invention is not particularly limited. Examples of the main compounds include natural rubber, polyisoprene, polybutadiene, poly (styrene-butadiene), polychloroprene, acrylic rubber, acrylonitrile / butadiene copolymer rubber, ethylene propylene non-copolymer rubber (EPM), and ethylene propylene diene. Copolymer rubber (EPDM), epichlorohydrin rubber,
Ethylene-vinyl acetate rubber, ethylene-acrylic rubber,
Examples include fluororubber, chlorosulfonated polyethylene, and mixtures thereof.

The hydroxyl-terminated isobutylene-based polymer and / or the isocyanate-terminated isobutylene-based polymer obtained by reacting the hydroxyl-terminated isobutylene-based polymer with the polyisocyanate compound, which characterizes the present invention, can be used without any reaction after the addition. Although it is also possible to express the characteristic of, it is possible to further improve the strength and the like by utilizing a terminal reactive group and performing a crosslinking reaction with a polymer compound or an isobutylene-based polymer. . together,
Performing a cross-linking reaction is preferable because it stabilizes the expression characteristics and improves problems such as bleeding from the composition. It is effective to add a silane coupling agent or a curing catalyst as needed in order to accelerate the crosslinking reaction. The silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter, referred to as a hydrolyzable silicon group) and a functional group other than the group. Examples of the hydrolyzable silicon group include those in which the substituent bonded to silicon is a hydrolyzable group. In particular,
Examples of the hydrolyzable group include the groups already exemplified, but a methoxy group and an ethoxy group are preferable from the viewpoint of the hydrolysis rate. The number of hydrolysable groups is 2 or more, especially 3
Or more is preferred.

Examples of the functional group other than the hydrolyzable silicon group include primary, secondary, and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. . Of these, primary, secondary, and tertiary amino groups, epoxy groups, isocyanate groups, isocyanurates, and the like are preferable, and isocyanate groups and amino groups are particularly preferable.

As specific examples of the silane coupling agent,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane,
Amino group-containing silanes such as γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane Silanes containing a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as riethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxy Carboxysilanes such as silanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane; γ-chloro Halogen-containing silanes such as propyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane;
γ-isocyanatopropylmethyldiethoxysilane,
Examples include isocyanate group-containing silanes such as γ-isocyanatopropylmethyldimethoxysilane. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are modified derivatives thereof, are also used as silane coupling agents. Can be used.

The silane coupling agent used in the present invention is:
It is used in the range of 0.1 to 10,000 parts based on 100 parts of the isocyanate-terminated isobutylene-based polymer obtained by reacting the hydroxyl-terminated isobutylene-based polymer and / or the hydroxyl-terminated isobutylene-based polymer with the polyisocyanate compound. In particular, it is preferable to use in the range of 1 to 100 parts. The silane coupling agent may be used alone or in combination of two or more.

Examples of the catalyst for accelerating the curing reaction include divalent and tetravalent tin-based curing catalysts, aluminum-based curing catalysts,
An amine-based curing catalyst may be used. 4 of these
Valent tin-based curing catalysts are preferred because of their high catalytic activity.
Tetravalent Examples of tin curing catalyst include tin carboxylates, dialkyl tin oxides, and the general formula _{(4), Q d Sn (} OZ) 4-d, or [Q ₂ Sn (OZ)] ₂ O (4) (wherein Q is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
Is a monovalent hydrocarbon group having 1 to 20 carbon atoms or S
represents an organic group having a functional group capable of forming a coordination bond with n. Further, d is 0, 1, 2, or 3. And the like. In addition, a tetravalent tin compound such as dialkyltin oxide or dialkyltin diacetate and a low-molecular silicon compound having a hydrolyzable silicon group such as tetraethoxysilane, methyltriethoxysilane, diphenyldimethoxysilane, or phenyltrimethoxysilane Reactants are also effective. Among these, compounds represented by the general formula (4), that is, chelate compounds such as dibutyltin bisacetylacetonate and tin alcoholates are preferable because of their high activity as catalysts.

Specific examples of the tin carboxylate include:
For example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethyl malate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin dibutyltin Examples include tridecyl malate, dibutyl tin dibenzyl malate, dibutyl tin maleate, dioctyl tin diacetate, dioctyl tin distearate, dioctyl tin dilaurate, dioctyl tin diethyl malate, dioctyl tin diisooctyl malate, and the like.

Specific examples of the dialkyltin oxides include dibutyltin oxide, dioctyltin oxide, and a mixture of dibutyltin oxide and phthalic acid ester.

Among these, dibutyltin bisacetylacetonate and dibutyltin dimethoxide are more preferred because of their low cost and easy availability.

A silanol condensation catalyst other than the above-mentioned tetravalent tin curing catalyst may be used. Specifically, a divalent tin-based curing catalyst such as tin octylate; an aluminum-based curing catalyst such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetonate; Lead octylate; butylamine, octylamine, laurylamine,
Dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-
Amine-based curing catalyst such as tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or Salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; γ-aminopropyltrimethoxysilane, N −
Silanol condensation catalysts such as silane coupling agents having an amino group such as (β-aminoethyl) aminopropylmethyldimethoxysilane; and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

These catalysts may be used alone.
Two or more kinds may be used in combination.

In the composition of the present invention, various additives such as a filler, a flame retardant, an ultraviolet absorber, an antioxidant, an antistatic agent, a lubricant, a pigment and the like are provided as long as the effects of the present invention are not substantially impaired. Can be added as needed.

The filler is compounded for the purpose of improving or increasing the mechanical strength and durability of the thermoplastic resin composition. Examples of such a filler include glass fiber,
Examples include glass beads, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica, quartz powder and the like.

Examples of the various additives include a hindered phenol-based antioxidant; a phosphorous antioxidant such as a phosphite ester and a phosphate ester; an antioxidant such as an amine antioxidant; Benzophenone-based ultraviolet absorbers; aliphatic carboxylic acid ester-based, paraffin-based external lubricants; organic tin-based compounds, organic lead-based compounds and other organic compound-based stabilizers; further, flame retardants, release agents,
Examples include an antistatic agent and a coloring agent.

The hindered phenolic antioxidants include, for example, 2,6-di-tert-butyl-p-cresol,
n-octadecyl-3- (4'-hydroxyl-3 ',
5'-di-tert-butylphenyl) propionate and the like are preferably used. Further, as the phosphorus-based antioxidant, tri (nonylphenyl) phosphite is used, and these may be used in combination with the hindered phenol-based antioxidant. It is also effective to add a tackifier resin for the purpose of imparting tackiness or surface modification to the composition. The tackifier resin is not particularly limited, and those usually used as a tackifier can be used. Specific examples include phenol resins, modified phenol resins, cyclopentadiene-phenol resins, xylene resins, cumarone resins, petroleum resins, terpene resins, terpene phenol resins, rosin ester resins, and the like. Of these, terpene resins and petroleum resins are particularly compatible,
It is preferable because the adhesive property is good. These may be used alone or in combination of two or more.

The amount of the tackifier resin to be used is generally 10 to 300 parts by weight, more preferably 30 to 150 parts by weight, per 100 parts by weight of the component (A). If the amount of the tackifier resin is less than 10 parts or more than 300 parts, the tack tends to be insufficient or the adhesive strength tends to be insufficient. However, the amount of the tackifier resin is not limited to this.

The composition obtained according to the present invention can be used for applications which can be usually used in the art, and is not particularly limited. For example, films,
Sheets, boards, synthetic leather, pipes, machinery and equipment parts, daily necessities, containers, building materials, foam products, reinforced products, molding materials, adhesives, adhesives, paints, automotive parts, electric and electronic parts, medical equipment and parts, Used for hoses, vibration insulators, belts, coupling materials, rolls, fibers, etc.

[0078]

EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 A 5000 ml separable flask was equipped with a three-way cock, a thermocouple, and a stirrer equipped with a vacuum seal, and the atmosphere in the flask was replaced with nitrogen. To this, 592 ml of toluene dehydrated with Molecular Sieves 3A and ethylcyclohexane 73.
6 ml was added, and 1,4-bis (1-chloro-1-) was further added.
Methylethyl) benzene (5.56 g, 24.0 mmol)
1), 2-methylpyridine (264 mg, 2.83 mm)
ol) and cooled to -70 ° C. After cooling, isobutylene monomer (120 ml, 1.44 mol) was introduced, and titanium tetrachloride (2.52 ml,
23.0 mmol) was added to initiate polymerization. At this time, the temperature was raised by about 15 ° C. The polymerization was completed in about 60 minutes (with this, no exothermic reaction system was observed). After the polymerization, 2,7-octadienyl acetate (32.4 g, 193 m
mol) and titanium tetrachloride (39.8 ml, 386 m
mol) was added. After the reaction for 5 hours, the reaction mixture was introduced into 1.5 L of ion-exchanged water heated to 80 ° C.
Stirring was performed for minutes. After standing, the aqueous layer was removed and 1 L of 2
An N sodium hydroxide aqueous solution and 10.0 g of tetrabutylammonium bromide were added, and the mixture was stirred at 100 ° C. for 12 hours. After completion of the reaction, the aqueous alkali solution is removed and 1 L
After washing three times with deionized water, the organic layer was isolated. 10 L of acetone was added thereto to reprecipitate the polymer, and low molecular compounds were removed. The precipitate was further washed twice with 1 L of acetone, and further dissolved in 500 ml of hexane. The solution was transferred to a 1 L mold flask, and heated under an oil bath (180 ° C.) under reduced pressure (final 1 Torr).
The solvent was distilled off according to the formula (1) below to obtain polyisobutylene having a desired hydroxyl group at the terminal. The obtained polyisobutylene was analyzed by gel permeation chromatography (GPC; standard polystyrene conversion method) and NMR.
This was performed using (GPC) LCModule1, GP made by Waters
C column; polystyrene cross-linked gel (shodex GP)
CK-804; manufactured by Showa Denko KK), developing solvent: chloroform. (NMR) Gemini-300 manufactured by Varian
Measurement solvent: carbon tetrachloride / acetone heavy = 4/1 mixed solvent,
Quantitative method; based on the signal of the initiator residue (7.2 ppm), the signal of methylene adjacent to the terminal hydroxyl group (4.
(00 ppm). Fn (CH ₂ O
H) is the amount of functional group introduced into the polymer terminal, and when quantitatively introduced, it is 2.0 for the initiator used this time. The analysis results of the obtained polymer are as follows. Number average molecular weight = 5600, molecular weight distribution = 1.2. The amount of hydroxyl groups introduced is as follows: Fn (CH ₂ OH) = 1.
90. Example 2 Hydroxyl-terminated polyisobutylene obtained in Example 1
5.90 g (22.5 mmol) of methylene diphenyl diisocyanate was added to 4 g (7.9 mmol), and the mixture was stirred and mixed at 100 ° C. for 2 hours under nitrogen to prepare an isocyanate-terminated polyisobutylene. Example 3 High-density polyethylene (HIZEX 2200 manufactured by Mitsui Chemicals, Inc.)
J) To 30.0 g, 1.74 g of the isocyanate-terminated polyisobutylene obtained in Example 2 was charged into a 500 ml separable flask into a device equipped with a stirrer equipped with a vacuum seal, and melt-mixed at 170 ° C. Done. After the obtained mixture was cooled to room temperature, it was 140 mm long and 80 m wide.
Press molding (5 minutes, 50 atm) was performed after preheating using a metal mold having a thickness of 3 m (thickness: 3 mm) to obtain a molded body. The molded body was cut into two using a cutter, and 140 mm x 40
mm was obtained. A cellophane adhesive tape (manufactured by SEKISUI, standard JISZ1522, 18) is applied to the obtained molded plate.
mm width) and left for 30 minutes.
Peeling speed 300mm / min under 3 ° C and 65% RH conditions
Was peeled off at 180 ° to measure the adhesive strength. The adhesive strength of the formed plate was 0.304 kgf. Comparative Example 1 A sample of polyethylene alone was obtained by molding and cutting only the high-density polyethylene used in Example 3 under the same conditions. The adhesive strength of the formed plate was 0.280 kgf. It was confirmed that the addition of the isocyanate-terminated isobutylene-based polymer changed the surface characteristics of the high-density polyethylene and improved the adhesion. Example 4 7.88 g of SEPS (Septon 2002 manufactured by Kuraray) as a thermoplastic elastomer, 2.03 g of an isocyanate-terminated isobutylene polymer obtained in Example 2, and a hydrocarbon-based process oil (PW-380 manufactured by Idemitsu Petrochemical)
3.94 g and 7.88 g of a petroleum resin-based tackifying resin (trade name: ALCON P-100 manufactured by Arakawa Chemical Industries, Ltd.)
Was heated to 80 ° C. and mixed with stirring. 3.70 g of hexane was added to the obtained mixture, and the mixture was stirred and mixed at room temperature. The resulting pressure-sensitive adhesive composition has a thickness of about 5 after drying.
Polyethylene terephthalate film having a thickness of 50 μm and subjected to a corona treatment to a thickness of 0 μm (manufactured by Toray Industries, Inc.)
And dried at room temperature for 1 hour to prepare an adhesive tape. The adhesive strength of the obtained adhesive tape was measured according to JIS Z-023.
The measurement was performed according to the following method in accordance with Example 7. Adhesive strength measurement method The obtained adhesive tape was cut into a width of 25 mm, and the adhesive surface of the adhesive tape was attached to a stainless steel plate (SUS # 304).
After standing for 30 minutes, the tensile tester was used at 23 ° C and 65% RH.
Under the conditions, 180 ° peeling was performed at a peeling speed of 300 mm / min to measure the adhesive strength. The adhesive strength was 1.14 kgf. At this time, no adhesive composition remained on the stainless steel. Further, even after the same sample was subjected to the peeling / adhering test 50 times repeatedly, it had adhesiveness, and the adhesive composition did not remain on the stainless steel at all. Comparative Example 2 A pressure-sensitive adhesive composition was prepared with the same composition except that the isocyanate-terminated isobutylene-based polymer in Example 4 was not included, and the same test was performed. The adhesive strength at this time is 0.84
Kgf. It was confirmed that the addition of the isocyanate-terminated isobutylene-based polymer further improved the adhesive properties of the thermoplastic elastomer-based adhesive. Example 6 Epicoat 828 manufactured by Yuka Shell Epoxy was used for 10.0
12.0 g of YH306 manufactured by Yuka Shell Co., Ltd. and 1.0 g of Epicure 3010 as a curing agent were added to the epoxy resin base material, and 0.5 g of the hydroxy-terminated isobutylene-based polymer obtained in Example 1 was used. The mixture was added and stirred and mixed at room temperature to prepare an epoxy resin composition. This composition was formed into a sheet having a thickness of about 3 mm and cured in an oven at 150 ° C. for 2 hours. This sample was cut at a width of 10 mm, and the flexural modulus was measured. Measurement is JISK72
03. The flexural modulus of the sample is 274
Kgf / mm2, maximum point stress is 6.69 Kgf / mm2
Met. Comparative Example 3 A sample was prepared in the same manner as in Example 6, except that the hydroxyl-terminated isobutylene-based polymer was removed, and the mechanical properties were measured. The flexural modulus of the sample was 265 kgf /
mm2, and the maximum point stress was 10.2 kgf / mm2. It was confirmed that the addition of polyisobutylene alleviated the stress without lowering the flexural modulus. From this fact, it became clear that the epoxy resin can be modified by adding hydroxyl-terminated polyisobutylene to the epoxy resin.

[0079]

According to the present invention, a hydroxyl-terminated isobutylene-based polymer and / or
Alternatively, by adding an isocyanate-terminated isobutylene-based polymer obtained by a reaction between a hydroxyl group-terminated isobutylene-based polymer and a polyisocyanate compound to a polymer compound, new properties can be imparted to the polymer material.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AC01W AC02W AC06W AC08W AC11W AC12W BB03W BB06W BB12W BB15W BB17W BB18X BB24W BB28X BC03W BC04W BC05W BC06W BC07W BC08W BC09W BD04W BD06W BD08W BD06W BD08W BD06W BD08W BD06W BD08W BD06W BD08W BD06W BD08W BP01W BP02W CB00W CC03W CC16W CC18W CD00W CD01W CD02W CD05W CD08W CD12W CD13W CD17W CF01W CF06W CF07W CF21W CG01W CG02W CH04W CH07W CK03W CK04W CL01W HC03 HCCM0412 HC03 HC03 HC03 DB03 HC03 HC07 HC64 HC67 HC71 HC73 JA42 MA11 MA12 MA21 MA22 MA24 MA26 QB10 QB14 QB17 QC01 RA02 RA03 RA08 RA09 RA10 RA11 RA12 RA14 RA15

Claims (7)

[Claims] (1) a polymer compound (excluding the polymer of component (B)), (B) a reaction between a hydroxyl-terminated isobutylene-based polymer and / or a hydroxyl-terminated isobutylene-based polymer and a polyisocyanate compound. A composition comprising the obtained isocyanate-terminated isobutylene polymer as an essential component. 2. The composition according to claim 1, wherein the polymer compound is one or more selected from the group consisting of a thermosetting resin, a thermoplastic resin, a thermoplastic elastomer, and a rubber. 3. A polymer compound (B) excluding a polymer of the component (B), 100 parts by weight of the polymer compound (B), a hydroxyl group-terminated isobutylene polymer and / or a hydroxyl group-terminated isobutylene polymer and a polyisocyanate. 3. The composition according to claim 1, comprising 0.1 to 100 parts by weight of an isocyanate-terminated isobutylene-based polymer obtained by reaction with the compound. 4. A polymer compound (B) excluding a polymer of the component (B), 100 parts by weight of (B) a hydroxyl-terminated isobutylene-based polymer and / or a hydroxyl-terminated isobutylene-based polymer and a polyisocyanate. The composition according to any one of claims 1 to 3, comprising 1 to 50 parts by weight of an isocyanate-terminated isobutylene-based polymer obtained by reaction with the compound. 5. The composition according to claim 1, wherein the polymer compound (A) (excluding the polymer of the component (B)) is a thermoplastic elastomer. 6. A polymer (B) having a hydroxyl group-terminated isobutylene-based polymer and / or a hydroxyl group-terminated isobutylene-based polymer per 100 parts by weight of a polymer compound (excluding the polymer of the component (B)). 1 to 50 parts by weight of the isocyanate-terminated isobutylene-based polymer obtained by the reaction with the isocyanate compound, and 10 to 150 parts by weight of the (C) tackifier.
The composition according to any one of claims 1 to 5, comprising 10 to 150 parts by weight of a plasticizer (D). 7. A hydroxyl group-terminated isobutylene-based polymer represented by the formula 1: R ¹ (AX) _a (1) (wherein R ¹ is a monovalent to tetravalent monocyclic or polyvalent aromatic ring having a plurality of aromatic rings). A hydrocarbon group, X is a chlorine or bromine group, a is an integer of 1 to 4. A is a polymer of one or more cationically polymerizable monomers, and the polymerizable monomer is at least isobutylene as an essential component. When a is 2 or more, A may be the same or different.) And a halogen-terminated isobutylene-based polymer obtained by cationic polymerization, and a compound represented by the formula 2: CH ₂ ＣC (R ² ) -B-OG (2) (wherein, R ² is hydrogen or a saturated hydrocarbon group having 1 to 18 carbon atoms, B is a divalent hydrocarbon group having 1 to 30 carbon atoms, and G is a protecting group for a hydroxyl group. Having a protected hydroxyl group at the terminal by the reaction with the compound represented by After producing the isobutylene-based polymer composition according to claim 1, characterized in that it is obtained by deprotecting the hydroxyl group 6.