JPS6286074A - Self-adhesive composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent tackiness, adhesion and creep resistance, which comprises a particular terminal modified block copolymer and a tackifier resin. CONSTITUTION:95-5wt% conjugated diene (e.g., isoprene) and 5-95wt% nl aromatic hydrocarbon (e.g., styrene) are polymerized in the presence of an (organic) alkali metal polymn. initiator (e.g., ethyllithium) to obtain a block copolymer having an MW of 5,000-1,000,000 having an alkali metal at least one terminal thereof. The terminal alkali metal of the copolymer is reacted with a terminal treating agent capable of forming, at the terminal of the polymer, a polar group-contg. atomic group contg. at least one atom selected from the elements belonging to Groups IV-VI of the periodic table and having an electronegativity (Xp) satisfying the equation (wherein N is a group number of the periodic table to which the atom belongs) (e.g., phthalic anhydride) to obtain a terminal modified block copolymer (A) having a terminal treating agent resiude. 100pts.wt. component (A) is blended with 40-200pts.wt. tackifier resin (B) (e.g., rosin ester).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an adhesive composition with excellent tackiness, adhesion and creep resistance, and more particularly, to an adhesive composition containing a conjugated diene and a vinyl aromatic hydrocarbon. The present invention relates to an adhesive composition comprising a terminal-modified block copolymer consisting of the above and a tackifier resin.

(Prior Art) Adhesives have heretofore been used for various purposes such as adhesive tapes and labels. Generally, adhesives are applied to tapes by applying an adhesive solution prepared by dissolving the adhesive in a solvent onto a base material by means of a roll, spray, or the like.

However, the use of solvents has many problems in terms of air pollution, fire, labor and the environment, hygiene, etc., and has recently become a serious social problem. Therefore, non-solvent type Botmelt adhesives have recently been attracting attention as a means to solve these inconveniences.

Base polymers for hot melt adhesives include ethylene/vinyl acetate copolymers, block copolymers of co-19 diene and vinyl aromatic hydrocarbons, and ethylene/α-
Various polymers such as olefin copolymers and polyester resins are used, but block copolymers tend to be particularly preferred because they have a relatively good balance between adhesiveness and creep resistance. . For example, Japanese Patent Publication No. 44-17037@ and Japanese Patent Publication No. 45-41518 disclose adhesive compositions using linear block copolymers such as polystyrene-polybutadiene-bolystyrene or polystyrene-polyisoprene-polystyrene. There is. Further, Japanese Patent Publication No. 56-49958 discloses a hot-melt adhesive composition using a branched block copolymer of (polystyrene-polybutadiene)nX.

(Problems to be Solved by the Invention) However, these compositions have the following drawbacks, and their performance as hot melt adhesives is still insufficient. That is, a block copolymer composed of styrene and butadiene has a low initial adhesive strength, and if a large amount of a softener is added to improve the initial adhesive strength, the creep resistance decreases. In addition, a block copolymer composed of styrene and isoprene has better initial adhesion than the block copolymers described above, but is inferior to the creep resistance of the block copolymers currently used in the field of adhesive tapes and labels. If adhesive tapes using adhesives with low creep resistance are used under stressful conditions, such as on the opening and closing parts of cardboard boxes, or in hot summer environments, the adhesive layer may shift. Since this causes trouble, its improvement is strongly desired.

(Means and effects for solving the problem) In view of the current situation, the present inventors have developed an adhesive composition containing a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon,
In particular, as a result of intensive investigation into ways to improve the creep resistance of hot-melt adhesive compositions and obtain compositions with excellent tack and adhesive properties, we found that the ends of the block copolymer molecular chains were treated with a specific end-treating agent. discovered that the purpose could be achieved by using a block copolymer modified with
This led to the present invention.

That is, the present invention provides (a) a block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, in which a block copolymer selected from Group 1V, Group V, and Group VI of the Periodic Table is provided at the end of the polymer; and a terminal-modified block copolymer having a terminal treatment agent residue containing at least one atom whose electronegativity is in the following range (in the above formula, Xp is the electronegativity of the atom, and N is the period of the atom). (b) a tackifier resin.

The present invention will be explained in detail below.

The terminal-modified block copolymer of component (a) used in the present invention is obtained by polymerizing a conjugated diene and a vinyl aromatic hydrocarbon in the presence of an alkali metal or an organic alkali metal as a polymerization initiator. It is produced by treating a block copolymer consisting of a conjugated diene containing an alkali metal and a vinyl aromatic hydrocarbon with a specific end treatment agent that reacts with the alkali metal at the end of the polymer.

The conjugated diene used in the present invention is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2
．． Examples include 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and particularly common ones include 1,3-butadiene and isoprene.

These may be used not only alone, but also as a mixture of two or more.

The vinyl aromatic hydrocarbons used in the present invention include styrene, O-methylstyrene, p-methylstyrene, p-t
ert-butylstyrene, 1,3-dimethylstyrene,
Examples include α-methylstyrene, vinylnaphthalene, and nylanthracene, among which styrene is particularly common. These may be used not only alone, but also as a mixture of two or more.

Examples of alkaline earth metals used as a polymerization initiator in the present invention include lithium, sodium, and potassium. Further, as the organic alkali metal compound, alkyl or aryl alkali metal compounds such as lithium, sodium, potassium, etc., and rust compounds with naphthalene, anthracene, etc. can be used.

Particularly suitable polymerization initiators include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds.

Specific examples of these include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, tert-butyllithium, hexamethylene dilithium, butadienyl dilithium, isoprenyl dilithium, etc. can give.

Any known method for producing a block copolymer consisting of a conjugated diene containing an alkali metal at at least one terminal and a vinyl aromatic hydrocarbon may be used, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-1982. 17
Examples include methods described in Japanese Patent Publication No. 979M, Japanese Patent Publication No. 45-31951, Japanese Patent Publication No. 32415-1974, and the like.

These are methods of block copolymerizing a conjugated diene and an aromatic hydrocarbon using an organic lithium compound or other initiator in a hydrocarbon solvent. -A), ,B+A
-8).

(In the above formula, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated diene. The boundary between the A block and the block is not necessarily clearly distinguished. Also, n is an integer of 1 or more.) or the general formula, [(B-A>n dipping
rwX[CB −A+−TB 1.7X.

[(A-8+7Ah1μ (In the above formula, A and B are the same as above, and X represents an initiator such as a polyfunctional organolithium compound.

m and n are integers of 1 or more. ) It is obtained as a radial block copolymer represented by:

In addition, in the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons means 50% by weight of vinyl aromatic hydrocarbons.
Indicates a copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene or a vinyl aromatic hydrocarbon homopolymer block containing the above, and a polymer block mainly containing a conjugated diene is a block containing more than 50% of conjugated diene. A copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon or a conjugated diene homopolymer block contained in the amount.

The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered.

The blower copolymer used in the present invention may be any mixture of block copolymers represented by the above general formula.

Particularly preferred block copolymers in the present invention are block copolymers containing at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of conjugated dienes. .

Hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, and isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane, or benzene, Aromatic hydrocarbons such as toluene, ethylbenzene, xylene, etc. can be used. Furthermore, when producing the block copolymer, a polar compound or a randomizing agent can be used.

Polar compounds and randomizing agents include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether, amines such as triethylamine and tetramethylethylenediamine, thioethers, phosphines, phosphoramides, alkylbenzene sulfonates, potassium and sodium Examples include alkoxides.

The block copolymer used in the present invention has a vinyl aromatic hydrocarbon content of 5 to 95% by weight, preferably 10 to 95% by weight.
It is 90% by weight, more preferably 15 to 85% by weight. Such a block copolymer exhibits properties as a thermoplastic elastomer when the vinyl aromatic hydrocarbon content is 60% by weight or less, preferably 55% by weight or less; If it exceeds 65% by weight, preferably 65% by weight or more, it exhibits properties as a thermoplastic resin.

In the present invention, a particularly preferred component (a> is 10 to 55% by weight of vinyl aromatic hydrocarbon-containing tetracarbon, preferably 15
It is a block copolymer of ~45% polymer. A hot melt adhesive composition containing such a block copolymer has particularly excellent initial adhesive properties. The molecular weight of the block copolymer used in the present invention is 5,000 to 1,000,00
0, preferably 10,000 to soo, ooo, more preferably 30,000 to 500,000.

The block copolymer containing an alkali metal at at least one end obtained by the method described above is then reacted with a specific end treatment agent that reacts with the alkali metal at the end of the polymer. The specific end-treating agent used in the present invention is such that after reacting with the alkali metal at the end of the polymer, the remaining base is bonded to the end of the polymer, and the remaining base is a member of groups IV, V, and V of the periodic table. It is a treatment agent that forms a polar group-containing atomic group that necessarily contains at least one atom selected from Group VI and whose electronegativity satisfies the range of the following formula.

If the end treatment agent residue does not have such atoms, or if the end treatment agent residue does not bond to the end of the polymer, the improvement in creep resistance is insufficient. The atoms contained in the terminal treatment agent residue are as follows. where Xp is the electronegativity of the atom,
In the present invention, Pauling's electronegativity (Chemistry Handbook Basic Edition, revised 2nd edition, p. 1288, published by Maruzen Co., Ltd.) is used. N
is the group number of the atom in the periodic table. Atoms that satisfy this requirement include nitrogen, oxygen, silicon, phosphorus,
These include sulfur, germanium, tin, and lead. Particularly preferred atoms in the present invention are nitrogen, oxygen, and sulfur having an Xo value of 2.5 or more.

Moreover, the polar group-containing atomic group as used in the present invention specifically refers to a polar group-containing atomic group that generally contains the above-mentioned atoms in any of the following structural units [I] to [VI].

[I]] hydrogen-containing polar group -3o3H, -3o2H, -3OH.

S.H. [I[] Nitrogen-containing polar group other than the above -NR2, =NH-, -N-, -CN.

-NCO, -0CN, -3CN.

-NC3, -CONR2, -CONR-[I [[] Epoxy group- or thioepoxy group-containing polar group [IVI carbonyl group- or thiocarbonyl group-containing polar group [V] syringe-containing polar group P+0R)2. -P-(-3R> 2.-P(-OR
)2゜[VI] M (any of Si, Ge, Sn, Pb) S polar group -MX3. -MX2R, -MXR, -MR3 (where X
is a halogen, R is a substituent such as an alkyl group or a phenyl group) These structural units may be adjacent to each other, or two or more of these structural units may be present in the same terminal treatment agent residue. Particularly preferred structural units are [I], [II] [1] or [
VI].

Examples of the terminal treatment agent that provides the above structural unit at the end of the polymer include carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, and carboxylic acid ester. basis,
Amide group, sulfonic acid group, sulfonic ester group, phosphoric acid group, phosphoric ester group, amino group, imino group, nitrile group.

Compounds having a pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfite group, isocyanate group, isodiocyanate group, etc. and halogen-containing silicon compounds,
A rogen-containing tin compound or the like is used.

The following compounds are given as specific examples.

Examples of alkylene oxides include ethylene oxide,
Propylene oxide, butadiene oxide.

Butene oxide, cyclohexene oxide, vinyl cyclohexene oxide 1, styrene oxide.

Allyl glycidyl ether, epichlorohydrin.

■ Epoxidized hydrocarbon polymers such as pibromohydrin, epoxidized polybutadiene, epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, tetraglycidyl metaxylene diamine, tetraglycidyl-1
, 3-bisaminomethylcyclohexane, tetraglycidyldiaminodiphenylmethane, triglycidyl-P-
Examples include aminephenol, triglycidyl-m-aminephenol, diglycidylaniline, diglycidylorthotoluidine, and the like.

Examples of alkylene sulfides include ethylene sulfide, propylene sulfide, butadiene sulfide, etc.
Examples include compounds corresponding to the alkylene oxides.

Examples of isocyanate compounds include ethyl incyanate, n-butyl isocyanate, n-decyl isocyanate, 2-<4-methylcyclohexyl)ethyl isocyanate, methyl isocyanate, propyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-tolyl isocyanate, n -pentyl isothiocyanate, 2-hexyl isothiocyanate,
Butenyl isothiocyanate, xylyl isothiocyanate, triisocyanate, diphenyl ether, triphenylmethane triisocyanate.

Included are benzene-1,2,4-triisocyanate, naphthalene-1,3,7-triisocyanate, and the like.

Included are m- or p-phenylene diisocyanate, diphenylmethane diisocyanate, bitolylene diisocyanate, dianisidine diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate.

Examples of imino compounds include N-butylidenebenzenesulfenamide, N-improdlidenebenzenesulfenamide, N-benzylidenebenzenesulfenamide, N-ethylidenebenzenesulfenamide, N-(α-phenylbenzylidene ) Benzene sulfenamide, N-(α-methylbenzylidene)benzenesulfenamide, N-trimethylsilylupenzaldimine, N-triphenylbenzaldimine, N-trimethylsilyl-(1-phenylpentylidene)amine, N -(1~phenylpropylidene)
-1,1-dimethyl-1-phenyl-silaneamine, N
-trimethylsilyl-ethylideneamine, tri(1-aziridinyl)phosphine oxide, tri(2-methyl-1aziridinyl)phosphine oxide, tri(2-
ethyl-3decyl-1aziridinyl)bosphin sulfide.

Examples include tri(2-phenyl-1aziridinyl)bosphine oxide, tri(2-methyl-3cyclohexyl-1aziridinyl)phosphine sulfide, and the like. 3,4.
Triaziridinyl-substituted triazines and triphostriazines containing 5 or 6 aziridinyl-substituted rings are also suitable. Specific examples of these compounds include 2,4,6-tri(
aziridinyl>1.3.5-triazine, 2,4.6-
Tri(2-methyl-1-aziridinyl)'1,3.5-
Triazine, 2,4,6-tri(1-aziridinyl>2
．． 4.6-dolphospher 1,3.5-triazine, 2
, 4,6-tri(2-methyl-n-butyl-aziridinyl>2,4,6-dolyphospher 1,3,5-triazine, etc.).

Examples of aldehyde compounds include acetaldehyde, propionaldehyde, imbutyrylaldehyde, n-caproaldehyde, acetothioaldehyde, propionthioaldehyde, isobutyrylthioaldehyde, valeraldehyde, benzaldehyde, decanal, eicosanal, 2- In addition to phenylbutanal, 3-methylbenzaldehyde, 4-cyclohexylbenzaldehyde, cyclohexanecarboxaldehyde, 3-phenylcyclohexanecarboxaldehyde, 1,4.7-naphthinetricarpoxyaldehyde, 1,7.

Compounds such as 9-anthracentric carboxyl 7-aldehyde 1,5-pentantricarboxaldehyde and similar polyaldehyde-containing aliphatic and aromatic compounds may also be mentioned.

Examples of ketone and thioketone compounds include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, isopropyl methyl ketone, dipropyl ketone, acetophenone, benzophenone, 4,4'-
Bis(diethylamino)benzophenone, 4,4'-bis(diethylamino)(thio)benzophenone, 4,4
'-Bis(dimethylamino)benzophenone, 4,4'
Bis(dimethylamine)(thio)benzophenone, 4,
4'-dimethoxybenzophenone, 4,4'-dimethoxy(thio)benzophenone, 4,4'-bis(dimethylamine)benzophenone, 4.

4'-bis(dimethylamino)(thio)benzophenone, acetylcyclohexane, cyclopentylketone, 1
-Cyclooctyl-2methyl-1-butanone, 1-phenyl-5-cyclohexyl-3-pentanone, 2-butanone, 3-decanone, 2,4-dimethyl-3-heptanone, cyclohexanone, cyclodecanone, 3-phenylcyclooctanone , cyclopentanone, P-dimethylaminobenzalacetophenone, 1,3bis(4'-dimethylaminobenzal)acetone, and the like.

Examples of esters having a carboxylic acid ester group include monobasic acids such as acetic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, benzoic acid, and phenylacetic acid; Oxalic acid, maleic acid, malonic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, sebacic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, diphenic acid, etc. dibasic acids, methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n
-butyl alcohol, sec-butyl alcohol, te
Examples include esters with alcohols such as rt-butyl alcohol, amyl alcohol, hexyl alcohol, octyl alcohol, phenol, and cresol.

In addition, as lactones, beta-propiolactone,
There are lactones corresponding to delta-ualerolactone, epsilon-caprolactone, and the following acids. , 2-
Methyl-3-hydroxypropionic acid, 3-hydroxynonanone or 3-hydroxypelargonic acid, 2-dodecyl-3-hydroxypropionic acid, 2-cyclopendel-
3-hydroxypropionic acid, 3-phenyl-3-hydroxypropionic acid, 2-naphthyl-3-hydroxypropionic acid, 2-n-pblue 3-cyclohexyl-3-
Hydroxypropionic acid, 2-phenyl-3-hydroxytridecanoic acid, 2-(2-methylcyclopentyl)-
3-hydroxypropionic acid, 2-methylphenyl-3
-Hydroxypropionic acid, 3-benzyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropionic acid, 2-methyl-5-hydroxyvaleryl acid, 3-cyclohexyl-5-hydroxyvaleryl acid , 4
-Phenyl-5-hydroxyvaleryl acid, 2-hebutyl-4-cyclo-pentyl-5-hydroxyvaleryl acid, 2-methyl-3-phenyl-5-hydroxyvaleryl acid, 3-(2- cyclohexylethyl)-5-hydroxyvaleryl acid, 2-(2-phenylethyl)-4
-(4-cyclohexylbenzyl)-5-hydroxyvaleryl acid, benzyl-5-hydroxyvaleryl acid, 3
-ethyl-5-isopropyl-6-hydroxycaproic acid, 2-cyclobenthyl-4-hexyl-6-hydroxycaproic acid, 3-phenyl-6-hydroxycaproic acid, 3-(3,5-diethyl-cyclohexyl)-5 −
Ethyl-6-hydroxycaproic acid, 4-(3-phenyl-propyl)-6-hydroxycaproic acid, 2-benzyl-5-isopdyl-6-hydroxycaproic acid, 7-
Phenyl-6hydroxy-6-octoenoic acid, 2,2-
Di(1-cyclohexenyl)-5-hydroxy-5-heptenoic acid, 2,2-dipropenyl-5-hydroxy-5-heptenoic acid, 2,2-dimethyl-4-propenyl-3-hydroxy-3,5-heptadienoic acid There are others.

Other examples include malachite green lactone, crystal violet lactone, 3-diethylamino-6-methylfluoran, 3-diethylamine-
Examples include 6-methyl-7-anisonofluorane.

Examples of compounds having an amide group include N,N-dimethylformamide, N,N-dimethylthioformamide, N,
N-dimethyl-N', N'-(P-dimethylamino)benzamide, N-ethyl-N-methyl-8-quinolinecarboxamide, N,N'-dimethylnicotinamide, N,N-dimethylmethacrylamide, N -Methylphthalimide, N-phenylphthalimide, N-acetyl-ε-caprolactam, N-methyl-ε-caprolactam, N, N, N', N'-tetramethylphthalamide, 10-acetylphenoxazine, 3°7- Bis(diethylamino)-10-benzoylphenoxazine, 10
-acetylphenothiazine, 3.7bis(dimethylamino)-10-benzoylphenothiazine, and the like.

Further, as urea compounds, N,N'-dimethylurea, N,
N diethyl urea, N, N'-dimethylethylene urea, N
, N, N', N', -tetramethylurea, N, N-
Linear urea compounds such as dimethyl-N', N'-diethylurea, N,N-dimethyl-N', N'-diphenylurea, 1,3-dimethyl-2-imidazolidinone, 1
, 3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)- 2 imidazolidinone, 1°3-di(2
-ethoxyethyl)-2-imidazolidinone, 1,3
Examples include cyclic urea compounds such as -dimethylethylenethiourea and N,N',N''-trimethylisocyanuric acid.

As carboxylic acid anhydrides, saturated or unsaturated aliphatic,
Examples include anhydrides of alicyclic or aromatic polycarboxylic acids.

Specifically, for example, aliphatic polycarboxylic acids such as maleic acid and succinic acid, phthalic acid, isophthalic acid, terephthalic acid, aromatic polycarboxylic acids such as pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and nadic acid. Examples include anhydrides of carboxylic acids such as alicyclic polycarboxylic acids, and dianhydrides include pyromellitic acid dianhydride, 2.3
, 6.7-naphthalenetetracarboxylic acid dianhydride, 3.3', 4.4'-diphenyltetracarboxylic acid dianhydride, 1,2,5°6-naphthalenetetracarboxylic acid, 2.2', 3°3 'Diphenyltetracarboxylic 2,3-bis(3,4-dicarboxyphenylpropane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3.

4,9,'10-perylenetetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 3.3',4,4'-benzophenonetetracarboxylic acid dianhydride, etc. can also be used.

Examples of the acid halides include acid halides of the above-mentioned basic acids and polybasic acids.

The amine group-containing compound is a tertiary amine-containing compound,
In addition to the above-mentioned tertiary amino group-containing compounds, nuclear-substituted styrene derivatives represented by the formula (wherein R1 and R2 are 01 to 018 alkyl groups, aralkyl groups, and aryl groups), such as dimethylaminoethylstyrene and dimethylaminoethylstyrene. , dimethylaminoethylstyrene, dioctylaminoethylstyrene, di2-ethylhexylaminoethylstyrene, dioctadecylaminoethylstyrene, and the like. In addition to these, further examples include dimethylaminoethyl acrylate, dimethylaminoethyl acrylate, dioctylaminoethyl acrylate, and the like. In particular, nuclear-substituted styrene derivatives are preferred.

Examples of pyridine derivatives include 2-vinylpyridine, 4-vinylpyridine, 4-benzoylpyridine, 2-acetylpyridine, and 4-pyridinecarboxylic acid methyl ester.

Examples of the nitrile group-containing compound include acetonitrile, propionitrile, benzonitrile, benzylnitrile, acetonitrile, N,N-dimethylamino-benzonitrile, N,N-dimethylamino-benzylnitrile, and the like. Examples of sulfonic acids and esters include benzenesulfonic acid, toluenesulfonic acid, anthraquinonesulfonic acid, and N.

Examples include esters of N-dimethylaminobenzenesulfonic acid, N,N=dimethyltriidine sulfonic acid, and alcohols.

Examples of phosphorus-containing compounds include trialkyl or triallylphosphite represented by (RO)3P, (RO)
Trialkyl or triallylphosphite represented by 3P->O, (RS) trialkyl or triallylphosphite represented by 3P, (RO)3P-)
Examples include trialkyl or triallyl thiophosphate represented by S. R is, for example, methyl, ethyl,
Examples include alkyl groups such as butyl, hexyl, 2-ethylhexyl, cyclohexyl, nonyl, decyl, lauryl, tridecyl, and suderyl, phenyl groups, and phenyl groups substituted with the alkyl groups described above.

Compounds containing silicon include halogenated silanes such as tetrachlorosilane, tetrabromide silane, trichloromethylsilane, dichlorodimethylsilane, and dichlorodiphenylsilane, as well as those containing hydrolyzable organic groups other than halogen. compounds - for example, tetraethoxysilane, triethoxymonochlorosilane, jetoxymonochloromonomethylsilane, triethoxymonomethylsilane, trimethoxymonomethylsilane, jetoxydimethylsilane, dimethoxydimethylsilane, dimethyldiacetoxysilane,
Examples include methyltriacetoxysilane, chloromethyltriethoxysilane and 3-chloropropyltriethoxysilane.

Compounds containing tin include tin tetrachloride, monobutyltin trichloride, tetramethoxytin, trimethyltin chloride, tributyltin chloride, trioctyltin chloride, tributyltin bromide, dibutyltin dichloride, dioctyltin dichloride, phenyltributyltin, and methoxytributyltin. , benzyltributyltin, diphenyldibutyltin, dimethoxydibutyltin, dibenzyldibutyltin, phenoxytributyltin, diphenoxydibutyltin, tricyclohexyltin chloride, dicyclohexyltin dichloride, tridodecyltin chloride, didodecyltin dichloride, triethyltin chloride, diethyltin dichloride, tripropyl Tin chloride, dipropyltin dichloride, butyldimethyltiniodide, butyldicyclohexyltin bromide, dibutylvinyltin bromide, diethylphenyltin bromide, triphenyltin chloride, diphenyltin dichloride, tri-tolyltin bromide, tri-m
-Tolyltin chloride, 1-2-5-xylyltin bromide, trimethoxytin chloride, dimethoxytin dichloride, triethoxytin bromide, diethyltin dichloride, triphenoxytin chloride, diethyltin dichloride, tribenzyltin chloride , dibenzyltin dichloride, pensylphenyltin dibromide, benzylphenyltin dichloride, trinaphthyltin dichloride, and the like. Particularly preferred tin compounds include compounds having one or two halogen-tin bonds in one molecule, one to three alkoxy-tin bonds, aryl-tin bonds, and benzyl-tin bonds in one molecule. It will be done. In addition, carbon dioxide gas, carbon disulfide, phosgene, etc. can also be used as terminal treatment agents.

In the present invention, the terminal treatment agent suitable for the present invention is such that the residue of the terminal treatment agent that is bonded to the polymer terminal after reacting with the alkali metal at the polymer terminal is a carboxylic acid group, a thiocarboxylic acid group, an amino group,
It is a compound containing an epoxy group, a pyridyl group, a phenylmethoxy group, a phenylthiomethoxy group, a silyl group containing a hydrolyzable group, an alkyl and/or phenyltin group, or a group that becomes an alkali metal base.

It is preferable to add the above-mentioned end-treating agent to all polymer ends to which alkali metals are bonded, but it depends on various reaction conditions such as the type of end-treating agent, polymer structure, solvent, reaction temperature, and reaction equipment. Coupling between polymer molecules may cause a reaction, and in such cases a terminal treatment agent is introduced into the center of the polymer molecule. However, in the present invention, if 15% or more, preferably 30% or more of the polymer ends to which alkali metals have been bonded are modified with the end treatment agent, the creep resistance is effectively improved.

The amount of the terminal treatment agent used in the present invention is 0.7 to 2 equivalents, preferably 0.7 to 2 equivalents relative to the alkali metal at the polymer terminal.
．． 9 to 1.3 equivalents, particularly preferably 1.0 equivalents.

The reaction temperature and reaction time can be adjusted over a wide range, but usually the reaction temperature is 15 to 115°C and the reaction time is 1 second to
Stay within 3 hours.

In the terminal-modified block copolymer thus obtained, it is also possible to add water, alcohol, or other Lewis acid to replace the alkali metal moiety with hydrogen. Incidentally, even when the terminal treatment agent exhibits anionic polymerizability with respect to the alkali metal catalyst, the amount used is preferably within the above range. It is not preferable if a large amount of the terminal treatment agent polymerizes to form a polymer block because the initial tackiness decreases.

The tackifier resin of component (b) used in the present invention is one conventionally used as a tackifier in hot melt adhesives, such as coumaron/indene resin, phenol resin, P-tert-butylphenol, Acetylene resin, phenol/formaldehyde resin, terpene/phenol resin, polyterpene resin, xylene/formaldehyde resin, synthetic polyterpene resin, aromatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, oligomers of monoolefins and diolefins, hydrogenation Hydrocarbon resin, hydrocarbon tackifying resin, polybutene, polyhydric alcohol ester of rosin, hydrogenated rosin, hydrogenated wood rosin, ester of hydrogenated rosin and monoalcohol or polyhydric alcohol, turpentine tackifier, etc. are required. can be lost. More specifically, those listed in "Rubber/Plastic Compound Chemicals" (Rubber Digest Company Line) can be used.

Particularly suitable viscosity 1°°1 imparting agents include terpene resins, aromatic modified terpene hydrocarbon resins, alicyclic saturated hydrocarbon resins,
These are rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, and modified aliphatic petroleum resin, and a composition with good initial tackiness can be obtained.

In the present invention, the tackifier resin as component (b) generally contains 100 parts by weight of the block copolymer as component (a).
It is used in an amount of 40 to 200 parts by weight, preferably 60 to 150 parts by weight. If the formulation of the tackifier resin is outside this range, the adhesive properties of adhesive tapes using the resulting adhesive composition will be poor, which is not preferable.

In the present invention, a softener (component (C)) can be used if necessary. The softening agent of component (C) is a petroleum-based softener, paraffin, a vegetable oil-based softener, a thermoplastic, etc. Specifically, the softeners listed in the above-mentioned "Rubber/plastic compounded chemicals" are used. can.

The softener (component (C)) is generally used in an amount of 150 parts by weight or less, preferably from 5 to 100 parts by weight, based on 100 parts by weight of the block copolymer (a).

If it exceeds 150% by weight, it is not preferable because the creep resistance of adhesive tapes using the resulting adhesive composition decreases.

In the present invention, the reinforcing resins include polystyrene, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, as well as relatively low molecular weight thermoplastic polyester resin, A thermoplastic resin such as a polyamide resin or a polyphenylene ether resin is used as the block copolymer of component (a) 100. Creep resistance and hardness can be improved by adding 50 parts by weight or less, preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, to the W part. If the amount of reinforcing resin exceeds 50 parts by weight, it is not preferable because the surface tackiness decreases.

In the present invention, various stabilizers such as phenol stabilizers, phosphorus stabilizers, sulfur stabilizers,
Amine stabilizers and mixtures of these stabilizers can be used.

The adhesive composition of the present invention may contain other conventional elastomers, such as natural rubber, as long as they do not lose their adhesive properties.
Synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, polyisoprene isobutylene rubber, polypentenamer rubber, etc. may be mixed.

(Effect of the invention) The adhesive composition of the present invention can be used for various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, back glue for fixing various light plastic molded products, back glue for fixing carpets, and fixing tiles. It can be used as backing glue, and is particularly effective for hot melt adhesive tapes and labels. Moreover, the adhesive composition of the present invention can be applied to plastics, rubbery substances, foams, metals, wood,
It can also be used as an adhesive for paper products, etc.

(Example) Examples are shown below, but these are representative of the present invention and do not limit the scope of the present invention.

In addition, the block copolymer consisting of a conjugated diene containing an alkali metal at the end and a vinyl aromatic hydrocarbon used in the following examples was produced in the following manner.

[Block copolymer (a)] In a nitrogen gas atmosphere, add n-hexane solution containing 15 parts by weight of 1,3-butadiene and 20 parts by weight of styrene.
- After adding 0.11 parts by weight of butyllithium and polymerizing at 70°C for 2 hours, an n-hexane solution containing 45 parts by weight of 1°3-butadiene and 1 part by weight of 9220 parts of methi was added and the mixture was heated at 70°C. Polymerization was carried out for 2 hours. The obtained polymer contained B containing 40% by weight of styrene with lithium bonded to one end.
It was a block copolymer with a -A-B-A structure.

(A indicates a polymer block mainly composed of styrene, B indicates a polymer block mainly composed of butadiene. The following (B) (
c) (Same as in example (d)) [Block copolymer mouth] In a nitrogen gas atmosphere, 0.1 part by weight of n-butyllithium was added to a cyclohexane solution containing 14 parts by weight of styrene, and the mixture was heated to 70'C. After polymerizing for 1 hour, a xane solution containing 72 parts by weight of 1,3-butadiene was added to
Polymerization was carried out at 0°C for 2 hours.

Thereafter, a cyclohexane solution containing 14-fold styrene was further added, and polymerization was carried out at 70° C. for 1 hour.

The obtained polymer was a block copolymer having an A-B-A structure and having a styrene content of 28% by weight, with lithium bonded to one end.

[Block copolymer (c)] In a nitrogen gas atmosphere, isoprenyl dilithium was added to a cyclohexane solution containing 60 parts by weight of 1,3-butadiene and 9230 parts by weight of methi, and polymerized at 70'C for 2 hours. . Thereafter, a cyclohexane solution containing 10 parts by weight of 1,3-butadiene was added, and polymerization was carried out at 70'C for 1 hour. The obtained polymer had a number average molecular weight of 60,000, a styrene content of 30% by weight, and B- with lithium bonded to both ends.
It is a block copolymer with an A-B-A-8 structure.

[Block copolymer (d)] In a nitrogen gas atmosphere, 0.08 parts of n-butyllithium was added to a cyclohexane solution containing 7.5 parts by weight of styrene.
After adding parts by weight and polymerizing for 1 hour at 70°C, a cyclohexane solution containing 84 parts of isoprene was added and the mixture was heated at 70°C.
Polymerization was carried out for 2 hours. Thereafter, a cyclohexane solution containing 7.5 parts by weight of styrene was added and polymerized for 1 hour at 70°C, and then a cyclohexane solution containing 1 part by weight of isoprene was added and polymerized for 30 minutes. The obtained polymer was a block copolymer containing styrene @ 15% by weight and having substantially an ABA structure.

Examples 1 to 27 and Comparative Examples 1 to 4 According to Table 1, various end treatment agents were applied to the block copolymer having lithium at the end of the polymer to the polymerization initiator used in the polymerization of the block copolymer. 3 at 70°C using an equivalent amount.
A terminally modified block copolymer was produced by reacting for 0 minutes.

In addition, after reacting the terminal treatment agent, diluted hydrochloric acid water was added to neutralize the reaction solution, and then 2,6-sheeter was added as a stabilizer.
0.5 parts by weight of each of t-butyl-4-methylphenol, tri(nonylphenyl)phos, and phite were added to 100 parts by weight of the block copolymer, and then the solvent was distilled off by heating.

Next, 100 parts by weight of the terminal-modified block copolymer, 100 parts by weight of aromatic modified terpene resin [YS Resin, TO-105 (registered trademark) manufactured by Joshi Yushi Co., Ltd.], 30 parts by weight of naphthenic oil, and U as a stabilizer. Tsu crank N5-7 (
1 part by weight of registered trademark) Iriuchi Shinko Kagaku Tl4I] at 180℃
A hot melt adhesive composition was prepared by melt-kneading.

The thus-ANed adhesive compositions were applied to kraft paper which had been treated on the back side to produce kraft adhesive tapes.

The initial adhesiveness (tack), peel strength, and creep resistance against stainless steel were measured for this kraft adhesive tape. Each measurement was carried out by the method shown below.

For the tack, an adhesive tape was fixed on a board having an angle of 30° C., and the ball Nα that stopped on the surface of the adhesive tape was measured by the J, DOW ball rolling method.

Tack measurements were made at 23°C. The peel strength was determined by adhering the adhesive tape and stainless steel plate so that the adhesive area was 25 m x 100 ywn, and peeling at a peeling speed of 300 m/mi at 23°C.
Measurement was performed by peeling off with the mouth (180' peeling).

Creep resistance was determined by adhering the adhesive tape and stainless steel plate so that the adhesive area was 25 # x 25 m, fixing the stainless steel plate, and applying a load of 1 kg to the adhesive tape below. This was determined by measuring the time until peeling.

The results are shown in Table 1, and it can be seen that the pressure-sensitive adhesive composition of the present invention containing the terminal-modified block copolymer has excellent creep resistance and is suitable as a hot-melt pressure-sensitive adhesive.

(Leaving space below) Table 1 (Note 1) The effect of terminal modification on creep resistance was determined by treating a block copolymer containing an alkali metal at the polymer end with methanol to bond hydrogen atoms to the polymer end. Judgment was made based on the peeling time of an adhesive tape using a copolymer (no terminal treatment agent residue containing atoms specified in the present invention was bonded to the polymer terminal).

◎: Peeling time exceeds 1.5 times the peeling time of the reference product.

O: Peeling time exceeds 1 or 2 times the peeling time of the reference product, 1
．． Less than 5 times.

△; Peeling time exceeds 1.0 times the peeling time of the reference product, 1
．． 2 times or less A similar pressure-sensitive adhesive composition was prepared and evaluated for use in hot-melt pressure-sensitive adhesive tapes. The results are shown in Table 2.

Incidentally, the creep resistance properties were evaluated in each Example based on the performance of a composition prepared using the polymer of Comparative Example 2 described above as a block copolymer.

(Margin below) Table 2 Example 33 100 parts by weight of the same terminal-modified block copolymer used in Example 2, 60 parts by weight of YS Resin A-1150 (registered trademark), ethylene vinyl acetate copolymer 15 parts by weight, 50 parts by weight of paraffin wax, stabilizer Tsucrak N
A pressure-sensitive adhesive composition was prepared by blending 3 parts by weight of 5-7 (registered trademark), and its adhesion to an aluminum plate, sail 15, and polyethylene was examined. As a comparative example, a similar pressure-sensitive adhesive composition was prepared using the same block copolymer as that used in Comparative Example 1 above instead of the terminal-modified block copolymer.

Adhesion with the above adherend is at a temperature of 115℃ and a load of 60KFI.
/ cm z adhesive area 25rrvnX 100trt
The peel test was conducted at a peel rate of 5 C) s/min and a temperature of 23°C.

The results are shown in Table 3.

(Margin below) Table 3 (”1)=K!j/25s Procedure Nefu Seisho (self-motivated) January 20, 1986

Claims (1)

[Scope of Claims] 1 (a) A block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon, which has a polymer selected from Groups IV, V, and VI of the Periodic Table at the end of the polymer. 0.41≦X_p/N≦0.60 (in the above formula, X_p is an atom (b) a tackifier resin; and N is the periodic table group number of the atom.