JPS62246904A - Terminal-modified block copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer which can give a tackifier composition excellent in tackiness, adhesiveness and creeping resistance, by reacting a block copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon with a specified terminal modifier. CONSTITUTION:A conjugated diene (a) is copolymerized with 5-95wt% vinyl aromatic hydrocarbon (b) in a hydrocarbon solvent in the presence of at least one polymerization initiator selected from among (organo)alkalis to obtain a block copolymer (A) having an alkali metal on at least either terminal and having a number-average MW of 5,000-1,000,000. Component A is reacted with 0.7-2 equivalent, per equivalent of the terminal alkali metal of component A, of a terminal modifier (B) selected from among imino compounds, cyanamide compounds, aziridinyl compounds, amide compounds and other tert. amino group-containing compounds (e.g., diphenylcyanamide) at 15-115 deg.C for 1sec-3hr to obtain the titled copolymer terminated with a residue of the amino group- or imide group-containing terminal modifier.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a terminally modified block copolymer in which an amino group- or imide group-containing terminal treating agent residue is bonded to the polymer terminal.

The terminal-modified block copolymer of the present invention is particularly effectively used to produce a pressure-sensitive adhesive composition having excellent adhesiveness, adhesion, and creep resistance.

(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, working environment, hygiene, etc., and is becoming regarded as a serious social problem in the Omi region.

Therefore, non-solvent type hot melt adhesives have recently been attracting attention as a means to solve these inconveniences.

Hora 1 - As base polymers for melt adhesives, ethylene/vinyl acetate copolymers, block copolymers consisting of conjugated dienes and vinyl aromatic hydrocarbons, ethylene/α-
Various polymers such as olefin copolymers and polyester resins are used, but black copolymers are particularly preferred because they have a relatively good balance between viscosity and creep resistance. There is a tendency. For example, Special Publication No. 44-17037 Tan Gazette, Special Publication No. 45-4151
No. 8 discloses an adhesive composition using a linear block copolymer such as polystyrene-polybutadiene-polystyrene or polysbrene-polyisoprene-polysbrene. Also, 1.4 Publication No. 56-49958 @ (Polybrene-Polybutadiene). A hot melt adhesive composition using a branched block copolymer of X is disclosed.

(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 this strength, the creep resistance decreases. In addition, a block copolymer composed of styrene and isoprene has better initial viscosity 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 an adhesive tape or the like using an adhesive with low creep resistance is used on the 11th floor where stress is applied, such as the opening/closing part of a cardboard box, or when used in a hot summer environment, 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 methods for improving the creep resistance of hot-melt adhesive compositions and obtaining compositions with excellent adhesiveness and adhesion ↑j1, we found that active f [at the end of the block copolymer molecular chain imino compound, cyanamide compound, aziridinyl compound, amide compound, or a third compound other than the above compound.
The inventors have discovered that the object can be achieved by reacting with at least one type of terminal treatment agent selected from compounds containing amino groups of 1Q and using a block copolymer with modified terminals of 1 q. .

By the way, many inventions regarding polymers containing terminal functional groups have already been disclosed. For example, many methods are known for attaching functional groups to the ends of liquid rubber or polybutadiene using anionic polymerization techniques. For example, Tokuko Showa 3
No. 7-8190, Special Publication No. 38-342, Special Publication No. 38-
23043@, Special Publication No. 1974-24174, Special Publication No. 1977
-15toa@ etc. discloses a method for producing a polymer containing a terminal functional group by reacting a polymer polymerized using an organic lithium compound or the like with carbon dioxide, an epoxy compound, a thioepoxy compound, or the like.

Further, US Pat. No. 3,471,431@ discloses a terminally sulfonated polymer obtained by reacting a block copolymer with a Rilton compound. US Pat. No. 3,838,108, US Pat. No. 4,070,344 @, etc. disclose amine-terminated polymers in which polyisocyanate or polyinthiocyanate is reacted at the terminal end of the peeling polymer.

U.S. Patent No. 4,244,862 discloses a coating composition and a printing ink composition in which an inorganic pigment is blended with a terminal polar group-containing polymer obtained by reacting a block copolymer pasting polymer with a polar group-containing compound. has been done.

Further, US Pat. No. 4,020,036 and US Pat. No. 4,330,449 disclose compositions in which a block copolymer having a carboxyl group at the polymer end is blended with thermosetting unsaturated polyester or asphalt. The above-mentioned known amine-terminated polymers use polyisocyanate or polyisothiocyanate as a modifier, but these compounds easily react with moisture in the air, causing operational problems.

However, polymers obtained by reacting at least one terminal treatment agent selected from imino compounds, cyanamide compounds, aziridinyl compounds, amide compounds, and tertiary amine group-containing compounds other than these compounds with the active terminals of block copolymers. A compound in which an amino group- or imide group-containing terminal treating agent residue is bonded to the combined terminal is a new compound described at the end of the literature, and it does not have the above-mentioned drawbacks, so it is easy to use and has great industrial significance.

Furthermore, the present invention provides a vinyl aromatic hydrocarbon obtained by using at least one selected from alkali metals or organic alkali metals as a polymerization initiator, with a content of 5 to 95% by weight and a number average molecular weight of 5,000 to 5,000. An imino compound, a cyanamide compound, an aziridinyl compound, an amide compound, or a tertiary amino compound other than the above compound is added to the active terminal of a block copolymer consisting of a co-IQ diene with a co-IQ of 1.000,00″0 and a vinyl aromatic hydrocarbon. It relates to a terminal-modified block copolymer obtained by reacting at least one type of terminal-treating agent selected from group-containing compounds, in which an amino- or imide-containing terminal-treating agent residue is bonded to the polymer terminal.

The present invention will be explained in detail below.

The terminal-modified block copolymer of the present invention is a conjugated diene containing an alkali metal at at least one terminal, which 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 vinyl aromatic hydrocarbon with a specific end treatment agent that reacts with the alkali metal at the end of the polymer.

The simple IQ diene used in the present invention is a diolefin having one pair of conjugated double bonds, such as 1°3-1 tadiene, 2-methyl-1,3-butadiene (isoprene),
Examples include 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hekyridine, 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, 0-methylstyrene, p-methylstyrene, p-te
rt-Bubblystyrene, 1,3-dimethylstyrene, α
-Methylstyrene, vinylpphthalene, vinylantragon, etc., among which styrene is particularly common. These may be used not only alone, but also as a mixture of two or more.

Examples of the alkali metals used as polymerization initiators in the present invention include thielium, 1-lium, and potassium. In addition, organic alkali metal compounds include lithium, notrium,
Chain compounds of alkyrules such as potassium with alkali metal compounds, naphthalene, anthrahine, etc. can be used.

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

Specific examples of these include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyrimethylenedilithium, butadienyldilithium, isoprenyldilithium. etc. can be mentioned.

Any known method may be used as a method for producing a copolymer consisting of a conjugated diene containing an alkali metal at at least one end and a vinyl aromatic hydrocarbon,
For example, Special Publication No. 36-19286 q, Special Publication No. 43-
Examples include methods described in Japanese Patent Publication No. 17979, Japanese Patent Publication No. 45-31951, Japanese Patent Publication No. 4B-32415@.

These are methods of block copolymerizing a conjugated diene and a vinyl aromatic hydrocarbon using a polymerization initiator such as an organolithium compound in a hydrocarbon solvent. A).

, [3+A-[3].

(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 dienes. The boundary between the A block and the B block is not necessarily clearly distinguished. (n is an integer of 1 or more) or the general formula, [([3-A>-y←iX, [(A-[3)〒h了X
[(B−A+−ili−B廿m+I×.

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

17 as a block copolymer represented by m and "1 is an integer of 1 or more."
In the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons is a copolymer block of vinyl aromatic hydrocarbons and conjugated diene containing 50% by weight or more of vinyl aromatic hydrocarbons and/or vinyl aromatic hydrocarbons. It refers to a single hydrocarbon polymer block, and a polymer block mainly composed of coj-didiene refers to a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing a conjugated diene in an amount exceeding 50% by market weight. Or a co-1 didiene homopolymer block.

The vinyl aromatic hydrocarbon in the copolymer block may be uniformly distributed or tapered. A plurality of uniformly divided portions and/or tapered portions may exist in each block.

The block copolymer used for producing the terminally modified block copolymer of the present invention may be any mixture of block copolymers represented by the above general formula.

In the present invention, the preferred block copolymer for 1k is a block copolymer containing at least two polymer blocks mainly composed of vinyl aromatic hydrocarbons and at least one polymer block mainly composed of conjugated diene. be. By using such a block copolymer, a pressure-sensitive adhesive composition with excellent creep properties can be obtained.

Hydrocarbon solvents include butane, pentane, bequinone,
Aliphatic hydrocarbons such as isopentane, heptane, octane, isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclobequinone, methylcyclohexylline, ethylcyclohexylline, or bemvin,
i~ Aromatic hydrocarbons such as luene, ethylbenpine, xylene, etc. can be used. Furthermore, when producing the block copolymer, a polar compound or a randomizing agent may be used.

As polar compounds and randomizing agents, ethers such as tetrahydrofuran, diethylene glycol dibutyether and diethylene glycol dibutyl ether, amines such as triethylamine and 7-tramethylethylenediamine, thioethers, phosphines, phosphoramides,
Examples include alkylbenpine sulfonates, potassium and sodium alkoxides, and the like.

The block copolymer used for producing the terminal-modified block copolymer of the present invention has a vinyl aromatic hydrocarbon content of 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to 90% by weight. 85% by weight of b. 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 the vehicle volume% is exceeded, preferably 65% hanging
In the above cases, the resin exhibits characteristics as a thermoplastic resin.

The molecular weight of the block copolymer used for producing the terminal-modified block copolymer of the present invention is 5,000 to 1.000,
000, preferably 10,000 to 800,000
, more preferably 30,000 to 500,000. When the molecular weight is less than 5.000, the strength is poor, and i, ooo, oo.

If it exceeds Kanji [it is unfavorable because it is inferior to compassion].

The block copolymer having a right-handed alkali metal at at least one end, which has been added by the above method, is then treated with an imino compound, a shear J mido compound, an aziridinyl compound, an amide compound, or a tertiary amino group-containing compound other than said compound. The polymer is reacted with at least one type of terminal treatment agent selected from the compounds to obtain a terminal-modified 1 [1] copolymer in which the residue of the terminal treatment agent containing an amino group or an imide group is bonded to the polymer terminal. If the 93 filler residues at the ends of the polymer are not bonded, a pressure-sensitive adhesive composition with excellent creep resistance cannot be obtained.

The imino compound is a compound having at least one (carbodiimide bond) in the molecule.

Specific examples include benzylideneaniline, anizal-7niline, 4-methoxybenzylidene-4-'1-buburaniline, 4-methoxybensylian-4-ahythoxyaniline, benzylideneethylamine, benzylideneazine, N-trimedelsilyl-benzylideneamine, N −
Triphenylsilyl-benzylideneamine, N-trimethylsilyl-(1-7enylbenzylidene)amine, N
-Butylidenebenzenesulfenamide, N-isopropylidenebenzenesulfenamide, N-benzylidenebenzenesulfenamide, N-ethylidenebenzenesulfenamide, N-(α-phenylbenzylidene)
Penpine sulfenamide.

Examples include N-(α-methylbenzylidene) penpinsulfinamide. In addition, as carbodiimides, diethylcarbodiimide, diethylcarbodiimide,
Dipropylcarbodiimide, dibutylcarbodiimide, dicyc[1hexylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, methylp[1pylcarbodiimide 1zylcarbodiimide donylbenzylcarbodiimide] Of these, particularly preferred are benzylideneaniline,
Anizalaniline, 4-methoxybenzylidene-4-n
-Bublaniline, 4-methoxybenzylidene-4-acetoxyaniline, N,N'-dicyclohexylcarbodiimide, N,N'-diphenylcarbodiimide, N-
Cyclohexyl-2-benzothiazylsulfenamide.

The cyanamide compound has at least one >N-
(A compound having a three-N bond, specifically, dimethyl cyanamide, diethyl cyanamide, dipropyl cyanamide, dibdel cyanamide, dim-1 silcyanamide, dicyclohexyl cyanamide, dibenzyl cyanamide, diphenyl cyanamide, methylpropyl cyanamide) cyanamide,
Examples include butylcyclohexyl cyanamide, ethylbenzyl cyanamide, propylphenyl cyanamide, and phenylbenzyl cyanamide. Among these, particularly preferred are dicyclohexyl cyanamide and diphenyl cyanamide.

An aziridinyl compound is a compound having at least one aziridinyl group in the molecule, specifically, a tri(
1-7 diridinyl) phosphine oxide, tri(2-
Methyl-1-aziridinyl>phosphine oxide, tri(2-ethyl-3-decyl-1-7diridinyl)bosphinyllphide, tri(2-)1nyl-1-aziridinyl)phosphine oxide, tri(2-methyl- 3
-cyclohexyl-1-aziridinyl)bosphinyl fluoride, 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)2,4.6-1-lyphosph7 1 p 3 e J triazine, 2,4.6
-tri(2-methyl-'1-butyl-aziridinyl>2
．． Examples include 4,6-triphosphor 1,3,5-triazine. Among these, particularly preferred are di(2-methyl-1-aziridinyl)phenylphosphine ox1oid, tri(2-methyl-1-aziridinyl)phenylphosphine ox1noid, and 2,4.6-tri(aziridinyl)1 , 3,5-triazine.

An amide compound is at least one in the molecule.

Specifically, N,N-dimethylformamide, N,N-dimethylnicotinamide, 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-acepurphenokylidine, 3,7-bis(diethylamino)-10-benzoylphenothiazine, 10-acetylphenobuazine, 3,
7-bis(dimethylamino)-10-benzoylphenothiazine, N-ethyl-N-methyl-8-quinolinecarboxamide, etc., as well as N,N'-dimethylurea, N,N
'-diethylurea, N,N'-dimethylethyleneurea,
N, N, N'. N'-tetramethylurea, N,
N, N', N'-tetramethylthiourea, N,N-
Examples include linear urea compounds such as dimethyl-N',N'-diebruurea, N,N-dimethyl-N', and N'-diphenylurea.

Among these, preferred amide compounds include N,N-dimethylformamide, N,N-dimethylthioformamide, N,N,N',N'-tetramethylurea,
, N, N', N'-tetramethylthiourea, N.

N'-dimethylnicobunamide, N,N-dimethyl-N
', N'' (P-dimethylamino)benzamide, 3.
Examples include 7-bis(dimethylamino)-10-penzoylphenobuazine and N-ethyl-N-methyl-8-quinolinecarboxamide.

Furthermore, other amide compounds include 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-meth4diethyl)-2-imidazolidinone, 1,3-di(2-ethoxyethyl)-2
-Imidazolidinone, 1,3-dimethylethylenebuurea, N, N', N''-trimethylisocyanuric acid, N.

Examples include cyclic urea compounds such as N',N''-triethyl isocyanuric acid.

Also, N-methylpyrrolidone, N-ethylpyrrolidone, N
- N-substituted lactams such as phenylpyrrolidone, N-methyl-ε-caprolactam, N-ethyl-ε-caprolactam, N-7hydryl-ε-caprolactam, caffeine, 1-phenyl-3-methylpyrazolone, antipyrine, N- Examples include dimethylaminoamppyrine, N-phenylpyrazolone, N,N'-diphenylindigo, cryptopine, and tropinone. Among the amide compounds,
Particularly preferred are cyclic urea compounds, N-substituted lactams, and other compounds in which an amide group is incorporated into the cyclic structure.

Further, preferred compounds having an amide group in the cyclic structure include N-methylpyrrolidone, N-ethylpyrrolidone,
1,3. -dimethyl-2-imidazolidinone, 1,3.
-diethyl-2-imidazolidinone, N-methyl-ε-
caprolactam, N-aretyl-ε-caprolactam,
N, N', N'-trimethylisocyanuric acid is mentioned. A tertiary amino group-containing compound other than the above compounds is a compound that has at least one specific functional group that reacts with an alkali metal at the end of a polymer and also contains at least one tertiary amino group, Furthermore, after reacting with an alkali metal at the end of the polymer, its residue is bonded to the end of the polymer. Here, the tertiary amino group is (R+ and R? are an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, a substituted aryl group, an aryl al 4 is a R group.
+ and R2 may be the same or different).

It is a functional group represented by or a cyclic amine group having the general formula >NR. However, in the present invention, pyridyl groups are not included in tertiary amino groups. Further, as the specific functional group that reacts with the alkali metal at the end of the polymer, those selected from the following general formula can be mentioned.

-MXoF<'3-o, -MR'3, (In the above formula, R is hydrogen, an alkyl group having 1 to 22 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms, and a cycloalkyl group having 6 to 22 carbon atoms.
aryl group, substituted aryl group, aryl: 1-l group, R' is the same as R or an alkoxy group, M is silicon or tin, X is halogen, Y is oxygen or sulfur, "1 is 1-
It is an integer of 3. However, compounds containing the above general formula as an amide group are excluded). Suitable functional groups include carbonyl group, thiocarbonyl group, ester group, thioester group, formyl group, buoformyl group, epoxy group, thioepoxy group, sulfinyl group, sulfonyl group, phosphite group, buAphosphite group, Examples include a phosphate group, a sulfate group, a vinyl group, and a vinylidene group.

Specific examples of the above compounds include the following compounds.

4.4゛-His(dimethylamino)benzophenone, 4
,4'-bis(diethylamino)benzophenone, 4,
4'-bis(dibutylamino)benzophenone, 4-dimethylaminobenzophenone, 4,4'-bis(dimethylamino)thiobenzophenone, 4,4'-bis(diethylamino)thiobenzophenone, 4,4'-bis (dibutylamine)thiobenzophenone, 4-dimethylaminothiobenzophenone, p-dimethylaminoben IJ”
Luatriphenone, 1,3-bis(4'-dimethylaminobenol)acetone, malachite green lactone, crystal violet lactone, 3-diebruamino-6-methylfluorane, 3-diebruamino-6
-Methyl-7-anisonofluorane, trobinone, cryptopine, higelin, hytrastin, lobelanine, tetraglycidyl metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexylline, tetraglycidylaminosif 1-nylmethane, Glycidyl
p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyl orthotlu-C dine, 2-diethylaminop[1-panrilton, 2-diebruaminobutanerilton, triethoxy-
Examples include (4-diethylaminobuble)silane, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and dioctylaminobublacrylate.

Among these, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(diethylamino)thiobenzophenone, p-dimethylaminobenzalaretophenone,
1.3-bis(4'-dimethylaminobenryyl)acetone is preferred.

In addition, the general formula (in the above formula, R'' is an alkyl group having 1 to 22 carbon atoms,
cycloalkyl group, arylalkyl group, aryl group,
(substituted aryl group, n is an integer of O to 6) can also be suitably used, and specifically, dimethylamino nibblestyrene, diethylaminoethylstyrene, dimethylaminonylstyrene, dioctylaminoethylstyrene, Examples include di-2-edylhexylaminoethylstyrene and diocdadecylaminoethylstyrene.

Behind this tertiary amine-containing compound, p-(2-dimethylaminoethyl)styrene, m-(2-dimethylaminoethyl)styrene, p-(2-diethylaminoethyl)
Styrene and m-(2-diethylaminonibl)styrene are preferred.

Note that the terminal treatment agent used in the present invention does not contain an isocyanate compound or a thioisocyanate compound.

The above-mentioned terminal treatment agent is preferably added to all polymer terminals to which alkali metals are bonded, but various reactions such as the type of terminal treatment agent, polymer structure, solvent, reaction temperature, and reaction equipment etc. Depending on the conditions, a coupling reaction may occur between polymer molecules, and in such cases, a terminal treatment agent is introduced into the center of the polymer molecules. However, in the present invention, if 15% or more, preferably 30% or more, and more preferably 60% or more of the polymer ends to which the alkali metal was bonded are treated with the end treatment agent, various properties described below can be achieved. The improvement effect was recognized.

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.
．． It is 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 1.
It is within the range of 3.

It is also possible to add water, alcohol, or other Lewis acid to the terminal-modified B[1 ivy copolymer thus prepared] to replace the alkali metal moieties with hydrogen. Incidentally, even when the terminal treatment agent exhibits anionic polymerizability with respect to the alkali metal catalyst, it is preferable that the product used be within the above range. If a large amount of the terminal treatment agent polymerizes to form a polymer block, this is not preferable because the initial tackiness decreases.

The terminal block copolymers of the present invention include polystyrene, polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-butene copolymers, and relatively low molecular weight thermoplastics such as ethylene-vinyl acetate copolymers. Thermoplastic↑4 resins such as polyester resin, polyamide resin, polyphenylene ether resin, natural rubber, synthetic polyisoprene rubber, polybutadiene rubber, styrene.
Elastomers such as butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, polyisobrene isobutrene rubber, polypentenamer rubber, etc. may be blended. In addition, reinforcing materials or fillers such as calcium carbonate, silica, carbon black, glass fiber, and clay, plasticizers such as professional wrestling oil, polyethylene glycol, and phthalic acid nyspur, phenolic stabilizers, phosphorus stabilizers, and sulfur stabilizers. , amine stabilizers and mixtures of these stabilizers, ultraviolet absorbers, colorants, pigments, asphalt, and the like may be added. Specifically, use too much of the chemicals listed in "Rubber Plus Book Compounded Chemicals" (Rubber Digest Volume 1).

The terminal-modified t/l block copolymer of the present invention can be effectively used particularly for pressure-sensitive adhesive compositions.

In preparing the adhesive composition, 40 to 200 parts by weight, preferably 60 to 150 parts by weight of tackifier resin, per 100 parts by weight of the terminally modified block comonolymer of the present invention,
The softener can be used in an amount of 0 to 150 parts by weight, preferably 5 to 100 parts by weight. If the tackifier resin formulation ψ is outside this range, the adhesive properties of adhesive tapes using the adhesive composition will be poor, and this is not preferred. In addition, if the amount of the softener exceeds 150% by weight, it is not preferable because the creep resistance of adhesive tapes using the adhesive composition will be lowered.

Tackifier resins include coumaron/indene resin, phenol resin, P-sec-butylphenol/ahithylene resin, phenol/formaldehyde resin, terpene/phenol resin, polyterpene resin, xylene/formaldehyde resin, synthetic polyterpene resin, aromatic type. Hydrocarbon resins, aliphatic cyclic hydrocarbon resins, monoolefin and diolefin oligomers, hydrogenated hydrocarbon resins, hydrocarbon tackifying resins, polybutene, polyhydric alcohol esters of rosin, hydrogenated rosin, hydrogenated wood rosin, Examples include esters of hydrogenated rosin and monoalcohols or polyhydric alcohols, and turpentine-based viscosity imparting agents.

In addition, examples of the softening agent include petroleum-based softeners (paraffinic oil, naphdenoid oil, aromatic oil, etc.), paraffin, vegetable oil-based softeners, plasticizers, etc. A thermoplastic resin or an elastomer can be added as necessary.

(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 as follows.

[Block copolymer (a)] In a nitrogen gas atmosphere, a solution containing 15 strands of 1,3-butadiene and 20 strands of styrene was added to
After adding 0.11 parts by weight of 1-butyllithium and polymerizing at 10°C for 2 hours, an n-hekyrin solution containing 45 parts by weight of 1,3-butadiene and 20 parts by weight of styrene was added and the mixture was heated at 70°C. Polymerization was carried out for 2 hours. The obtained polymer was a styrene-containing ff+ block copolymer with 40% by weight B-A-B-A structure in which lithium was bonded to one end.

(A indicates a polymer block mainly composed of styrene, and B indicates a polymer block mainly composed of butadiene.
The same applies to example (c)) [Block copolymer (b)] In a nitrogen gas atmosphere, add 0.1 parts by weight of ``)-butyl lithium to a cyclohexylline solution containing 14 parts by weight of styrene, After polymerizing at 70°C for 1 hour, a cyclohekirin solution containing 72 parts of 1,3-butadiene was added.
Polymerization was carried out at 0°C for 2 hours. Thereafter, a cyclohekiline solution containing 14 parts of methicine was further added, and polymerization was carried out at 70°C for 10) minutes.

The 17-armed polymer was a block copolymer with an A-B-A structure having a styrene content of 28 wt% and having lithium bonded to one end.

[Block copolymer (c)] In a nitrogen gas atmosphere, spray 0.0.
After adding 8 parts by weight and carrying out monopolymerization for 1[li] at 70°C, a cyclohekirin solution containing the most 284 parts of styrene was added and polymerization was carried out at 0°C for 2 (14).
Add a cyclohexane solution containing 5 parts by volume and heat to 70°C.
After polymerization for 1ff), a cyclohekirin solution containing 1 part by weight of isoprene was added and the mixture was polymerized for 30 minutes. (The obtained polymer was a block copolymer containing 15% styrene and substantially having an A-B-A structure.

Examples 1 to 21 and Comparative Examples 1 to 3 Polymerization initiation using various end treatment agents for block copolymers having lithium at the end of the polymer according to Tables 1 to 3 A terminally modified block copolymer was produced by using one molecule per one lithium atom of the agent and reacting at 70° C. for 30 minutes.

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

Next, 100 parts by weight of the terminal-modified block copolymer, 100 parts by weight of aromatic modified I-rubene resin [YS Resin, TO=105 (registered trademark) manufactured by Yasukawa Oil Co., Ltd.], 30 parts by weight of naphthenic A-il, and stable As an agent, 1 monomer of [TSUKRAK N5-7 (registered trademark) produced by Jinnai Shinko Kagaku] was dissolved in WA at 180°C.
A hot melt adhesive composition was prepared by kneading.

Craft adhesive tapes were prepared by applying the pressure-sensitive adhesive compositions thus produced onto kraft paper which had been treated on the back side.

The initial adhesion (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 plate having an angle of 30° C., and the ball Nα that stopped on the surface of the adhesive tape was measured using the ball rolling method of J. Dow.

Tack measurements were made at 23°C. Peel strength is determined by adhesive tape and stainless steel plate bonding area 25JIlllIX 10
0 m, and peeled off at 23°C at a peeling rate of 300 m.
The measurement was performed by peeling (180° peeling) at the m/mi opening.

Creep characteristics were determined by adhering an adhesive tape and a stainless steel plate so that the contact area was 25×25, fixing the stainless steel plate, placing I kg of yuzu on the lower adhesive tape, and testing the adhesive tape at an ambient temperature of 60°C. This was determined by measuring the time required for complete peeling.

The results are shown in Tables 1 to 3, and it can be seen that the adhesive composition containing the terminal-modified block copolymer of the present invention has excellent creep properties and is suitable as a hot melt adhesive.

Table 1 Table 2 Table 3a Examples 22 to 26 In Example 8, an adhesive composition similar to Example 8 was prepared except that the tackifier resin shown in Table 4 was used. , and was evaluated for use in hot melt adhesive tapes. The results are shown in Table 4.

Incidentally, the creep 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.

(Leaving space below) Table 4 (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 vA time of the adhesive tape using the copolymer (polymer of Comparative Example 2).

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

○; The peeling time between 1tt5 and 1.2 of the standard product is Δ;
The peeling time exceeds 1.0 times the peeling time of the reference product, 1.2
X: Less than or equal to 1.0 times the peeling time of the reference product Example 27 and Comparative Example 4 The same terminal-modified block copolymer used in Example 7 was used with 100,000 parts of YS resin A- 60 parts by weight of 1150 (registered trademark), 15 parts by weight of ethylene-vinyl acetate comonolymer, 15 parts by weight of paraffin wax, stabilizer Tsurak N
A pressure-sensitive adhesive composition was prepared by blending 5-7 (registered trademark) in three parts. Adhesion to polyethylene was investigated. 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 was performed at a temperature of 115℃ and a load of 16ONg/
cttt, adhesion area 25# x 100 am, adhesion thickness 0.25mm, and peeling test was performed at a peeling rate of 50sn/m.
in, at a temperature of 23°C.

The results are shown in Table 5.

Table 5 (*1) = Kff/25 (Effects of the Invention) The terminally modified block comonomer of the present invention can be used for various purposes by taking advantage of the reactivity of the terminal amino group or imide group. For example, mechanical parts, small automatic parts, electrical parts, toys, industrial parts, belts, hoses, footwear, medical supplies, anti-pregnancy rubber, daily necessities, ['! Examples include building materials, sheets, films, adhesives, adhesives, and adhesive layer materials for laminated products. In particular, the sticky agent composition using the terminal-modified block copolymer of the present invention can be used for various adhesive tapes and labels, pressure-sensitive thin plates, pressure-sensitive sheets, backing glue for various types of light plus deck molded products, and backing for fixing carpets. Glue, backing glue for fixing tiles, plus book,
It can be used to bind rubber-like materials, foam, metal, wood, paper products, etc.

Claims (1)

[Claims] 1, the content of vinyl aromatic hydrocarbon is 5 to 95% by weight, the number average molecular weight is 5,
An imino compound, a cyanamide compound, an aziridinyl compound, an amide compound, or a tertiary amino group-containing compound other than these compounds is added to the active terminal of a block copolymer consisting of a conjugated diene vinyl aromatic hydrocarbon having a molecular weight of 000 to 1,000,000. A terminal-modified block copolymer obtained by reacting at least one type of terminal treatment agent selected from the following, and in which an amino group- or imide group-containing terminal treatment agent residue is bonded to the polymer terminal.