JP3504601B2 - Adhesive additives and hot melt adhesives - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to adhesive additives and hot melt adhesives. For more details, rubber,
The present invention relates to an additive for improving compatibility / plasticizer retention for an adhesive, which comprises a tackifying resin and a plasticizer, and a hot melt adhesive using the additive.

[0002]

2. Description of the Related Art Conventionally, hot-melt adhesives used for bonding polyolefin films, non-woven fabrics, resin molded products, etc. have been styrene-ethylene-propylene-styrene block copolymer rubbers or styrene-butadiene-styrene block copolymers. It is known that rubber is mixed with a tackifying resin component and a liquid plasticizer such as process oil (for example, Japanese Patent Laid-Open No. 3-1600).
83 and JP-A-8-60121).

[0003]

However, when the above-mentioned materials are used as hot-melt adhesives, the open time (the time between application and adhesion, which is possible for adhesion) is lengthened, and the melt viscosity is lowered. However, there is a problem that the cohesive force and the holding force are lowered, and the adhesive force to an adherend such as an olefin resin molded article is lowered. Further, there is a problem that the liquid plasticizer exudes to the adherend with time.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors to solve these problems and obtain an adhesive having excellent adhesive force and cohesive force and good plasticizer retention, the present invention Reached That is, the present invention relates to an additive for an adhesive consisting of rubber, a tackifying resin and a plasticizer, a styrene monomer (a1) selected from the group consisting of styrene, α-methylstyrene and a styrene derivative, and having 4 to 20 carbon atoms. Of aliphatic or alicyclic unsaturated hydrocarbons (a
2) and the alkyl or alkenyl group has 4 carbon atoms
To 24 alkyl or alkenyl (meth) acrylate (a3) as an essential constituent monomer, (a1),
Based on the weight of the copolymer (A) having (a2) and (a3) as essential constituent monomers, (a1) is 25 ≦ (a
1) <75% by weight, (a2) 15 ≦ (a2) <65% by weight, (a3) 10 <(a3) ≦ 60% by weight, number average molecular weight of 500 to 10,000, glass transition Temperature (Tg) is below 20 ° C and solubility parameter (S
Addition agent for improving compatibility / plasticizer retention characterized by containing a copolymer (A) having a P value of 7.5 to 9.5; hot melt adhesion containing the additive Agent; and an adhesive body of a polyolefin-based resin molded article adhered with the adhesive.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The styrene monomer (a1) constituting the copolymer (A) in the adhesive additive of the present invention.
Is selected from the group consisting of styrene, α-methylstyrene and styrene derivatives. As the styrene derivative, alkyl styrene having 1 to 4 or more carbon atoms in the alkyl group, halogenated styrene, amino group-containing styrene and divinylbenzene are used. Examples of the alkyl styrene include vinyltoluene, ethylstyrene, t-butylstyrene and the like.
Examples of the halogenated styrene include chlorostyrene, bromostyrene, fluorostyrene and the like. Examples of amino group-containing styrene include N,
Examples thereof include N-dimethylaminostyrene and N, N-diethylaminostyrene. Of these, preferred are styrene and α-methylstyrene,
More preferred is styrene.

Specific examples of the aliphatic or alicyclic unsaturated hydrocarbon (a2) having 4 to 20 carbon atoms (preferably 4 to 16) include aliphatic unsaturated hydrocarbons [monoolefin (for example, 1-butene, 4-methyl-1-pentene, 1-pentene, 2-pentene, 1-octene, 1-decene, 1-
Dodecene), diene (for example, butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-
Pentadiene, 2-methyl-1,3-pentadiene,
1,3-hexadiene, 1,4-hexadiene, 4,5
-Diethyl-1,3-octadiene, 3-butyl-1,
3-octadiene, etc.)]; alicyclic unsaturated hydrocarbons [mono- or di-cycloalkadiene (eg, cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, ethylidene norbornene, vinylidene norbornene, etc.)]; and these 2 Mixtures of more than one species are mentioned. Among these, more preferred are aliphatic dienes having 4 to 12 carbon atoms and alicyclic dienes having 5 to 14 carbon atoms, and particularly preferred are butadiene, dicyclopentadiene and ethylidene norbornene.

Specific examples of the alkyl or alkenyl (meth) acrylate (a3) having 4 to 24 carbon atoms in the alkyl or alkenyl group include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Examples include lauryl (meth) acrylate, myristyl (meth) acrylate, stearyl (meth) acrylate and oleyl (meth) acrylate. Of these, preferred are those in which the alkyl group has 4 to 18 carbon atoms.
Of alkyl (meth) acrylates, and particularly preferred is stearyl (meth) acrylate.

(A) is (a1), (a2) and (a)
If necessary, other monomer (a4) can be copolymerized with 3). Specific examples of (a4) include a hydroxyl group-containing (meth) acrylate [having 4 to 5 carbon atoms.
0, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyoxyalkylene (C2-4) glycol (polymerization degree 2-10 or more) mono (meth) acrylate, etc.]; Amino group-containing (meth) acrylate [C4
To 12, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.]; unsaturated carboxylic acid [C3 to 22, for example, (meth) acrylic acid, crotonic acid, (anhydrous) maleic acid, fumaric acid , (Anhydrous) itaconic acid, monoalkyl (carbon number 1 to 20) esters of these dicarboxylic acids, etc.]; (meth) acrylates other than the above-mentioned (a3) [for example, alkyl group having 1 to 3 carbon atoms (meta). ) Acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc.], alicyclic alkyl (meth) acrylate [carbon number 8 to 16,
For example, cyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, etc.], aralkyl (meth) acrylate [C9-21, for example, benzyl (meth) acrylate, etc.]; epoxy group-containing (meth) acrylate [C5 -18, for example, glycidyl (meth) acrylate, etc .; Dialkyl (C1-20) ester of the above unsaturated dicarboxylic acid (maleic acid, fumaric acid, etc.) [C6-C4, such as diethyl maleate, dibutyl fumarate] Etc.]; Imidized product of unsaturated dicarboxylic acid [C4-20, for example, maleimide, N-methylmaleimide, N-butylmaleimide, N
-Phenylmaleimide and the like]; and a mixture of two or more thereof. Among these, preferred are unsaturated carboxylic acids, alkyl (meth) acrylates having an alkyl group having 1 to 3 carbon atoms, and dialkyl esters of unsaturated dicarboxylic acids, more preferably (meth) acrylic acid and maleic anhydride. , Ethyl methacrylate and dialkyl maleate (1 to 20 carbon atoms) esters.

The amount of (a1) is usually 25 ≦ (a1) <75% by weight, preferably 30, based on the weight of (A).
≦ (a1) ≦ 65% by weight. If the amount of (a1) is less than 25% by weight, the cohesive force and holding power of the adhesive obtained by compounding will decrease, and if it is 75% by weight or more, the adhesive obtained by compounding will become hard and the adhesiveness will decrease. The amount of (a2) is
Based on the weight of (A), usually 15 ≦ (a2) <65% by weight, preferably 20 ≦ (a2) ≦ 55% by weight.
When the amount of (a2) is less than 15% by weight, the adhesive obtained by compounding becomes hard and the adhesiveness is lowered, and when it is 65% by weight or more, sufficient resin strength of the adhesive obtained by compounding cannot be obtained.

The amount of (a3) is usually 10 <(a3) ≦ 60% by weight, preferably 15%, based on the weight of (A).
≦ (a3) ≦ 50% by weight. When the amount of (a3) is 10% by weight or less, the adhesive obtained by compounding becomes hard and the adhesiveness is lowered, and when it exceeds 60% by weight, sufficient resin strength of the adhesive obtained by compounding cannot be obtained. . The amount of (a4) is
Based on the weight of (A), usually 0 or 0.1 ≦ (a
4) ≤ 10% by weight, preferably 0 or 0.2 ≤ (a
4) ≦ 5% by weight. Further, the total weight% of (a2) and (a3) in the copolymer (A) is preferably 25 to 60% by weight, more preferably 30% by weight, based on the weight of (A), from the viewpoint of plasticizer retention. ~ 50% by weight.

The copolymer (A) can be obtained by polymerizing the above-mentioned constituent monomers by a known method such as solution polymerization or bulk polymerization. The manufacturing method is not particularly limited, but the following method can be exemplified. (1) A copolymer obtained by continuously or intermittently supplying a monomer to a heated solvent in the presence of a polymerization initiator, and distilling off the solvent and, if necessary, unreacted monomer under normal pressure or reduced pressure after the polymerization. To obtain (solution polymerization method). Examples of the solvent used in the solution polymerization method include aromatic hydrocarbons (toluene, xylene, cumene, etc.), aliphatic hydrocarbons (n-hexane, n-octane, n-decane, etc.), alicyclic hydrocarbons (cyclohexane). , Methylcyclohexane, etc.), halogen-containing systems (chloroform, carbon tetrachloride, dichloroethane, etc.), ketones (acetone, methyl ethyl ruketone, etc.), ethers (dioxane, dibenzyl ether, etc.), esters (ethyl acetate, isopropyl acetate, acetic acid) Butyl) and the like.

(2) A polymerization initiator is added to a solution prepared by dissolving a monomer alone or a copolymer obtained by preliminarily polymerizing in a monomer, and heating this to polymerize it. A method of obtaining a copolymer by distilling off under reduced pressure (bulk polymerization method). (3) Polymerization in one or more kinds of melts selected from (B), (C) and (D), which are constituents of the hot melt adhesive described below, or in a solution obtained by adding the above solvent to the melt. In the presence of an initiator, the monomers are continuously or intermittently supplied to polymerize, and after the completion of the polymerization, the solvent and unreacted monomers are distilled off under atmospheric pressure or reduced pressure, if necessary, from the copolymer and other components. To obtain a mixture (co-polymerization method).

The polymerization temperature in the above solution polymerization method, bulk polymerization method or coexisting polymerization method is usually in the range of 80 to 240 ° C., and is appropriately selected depending on the kind of the polymerization initiator to be used, its amount and the desired molecular weight. can do. The end point of the reaction can be confirmed by measuring the amount of unreacted monomer at the time of polymerization using gas chromatography.
The temperature for distilling off the solvent or the unreacted monomer varies depending on the kind of the monomer, but is usually 100 to 200 ° C. Among the above-mentioned polymerization methods of the copolymer (A), the coexistence polymerization method is preferable from the viewpoint of compatibility.

Examples of the polymerization initiator used for producing the (co) polymer (A) include azo type polymerization initiators and organic peroxide type polymerization initiators usually used for radical polymerization. Examples of the azo-based polymerization initiator include 2,
2'-azobisisobutyronitrile, 2,2'-azobis (2,4 dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile) and the like can be mentioned.

Examples of the organic peroxide type polymerization initiator include peroxyketal [2,2-bis (4,4)
4-di-t-butylperoxycyclohexyl) propane, 1,1 bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,3
5-trimethylcyclohexane etc.)], hydroperoxide (t-butyl hydroperoxide etc.), dialkyl (C 1-12) peroxide (di-t-butyl peroxide, dicumyl peroxide etc.), diacyl peroxide (Lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, etc.), peroxyester (t-butylperoxybenzoate, t-hexylperoxyisopropyl monocarbonate, di-t-butylperoxyhexahydroterephthalate, etc.), per Organic peroxides such as oxydicarbonates (di-n-propylperoxydicarbonate and the like) can be mentioned. Among these, preferred are organic peroxide-based polymerization initiators, more preferred are dialkyl peroxides and peroxyesters, and particularly preferred are di-t-
Butyl peroxide, dicumyl peroxide and t-butyl peroxybenzoate. The amount of the polymerization initiator used is 0.01 to 20 with respect to the total weight of the monomers.
% Is preferable, and 0.05 to 15% is more preferable.

In producing the copolymer (A), a chain transfer agent may be used if necessary in order to adjust the molecular weight. Examples of chain transfer agents include, for example, α-olefins (eg 1-dodecene etc.), mercaptans (eg t-butyl mercaptan, n-dodecyl mercaptan etc.), disulfides (eg bis-2-amino-phenyl disulfide, diisopropyl xanthate). Gendisulfide, etc.), diazothioether (eg p-methoxyphenyldiazothio-2-naphthylether etc.), organic halides (eg carbon tetrachloride, carbon tetrabromide, chloroform etc.) and the like, which have chain transfer constants. 0.01
The above is preferable. The amount of the chain transfer agent used is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total weight of the monomers.

Differential scanning calorimetry (DS) of copolymer (A)
The glass transition temperature (Tg) according to the method C) is usually 20 ° C or lower, preferably -100 to 10 ° C, and more preferably-.
It is 60 to 0 ° C. When Tg exceeds 20 degrees, the adhesive obtained by blending (A) becomes hard and the adhesive strength at low temperature tends to decrease.

Number average molecular weight (Mn) of copolymer (A)
Is usually 500 to 10,000, preferably 1,000.
~ 5,000. When Mn is 500 or less, the cohesive force and holding power of the adhesive become weak, and when it exceeds 10,000, the compatibility with the rubber (B) becomes poor and the adhesive strength decreases. Further, the weight average molecular weight (Mw) of the copolymer (A)
Is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and Mw / Mn is preferably 1.2 to 2.5, more preferably 1.3 to 2.
It is 0. The Mn and Mw are gel permeation chromatography (GP) using polystyrene as a standard.
C) The value obtained by the method.

Solubility parameter of copolymer (A) (S
P value) is usually 7.5 to 9.5, preferably 7.8 to
It is 9.0, and particularly preferably 8.0 to 8.5. When the SP value is less than 7.5 or more than 9.5, the compatibility with the rubber (B) and the plasticizer (D) may be deteriorated, the adhesive force may be lowered, and the plasticizer retention may be deteriorated. The SP value is Fe
dors method [Polym. Eng. Sci. 14 (2)
152, (1974)].

The compatibility-improving / plasticizer-retention-improving additive for the adhesive of the present invention containing the copolymer (A) may optionally contain an antioxidant {hindered phenol compound [eg Pentaerythyl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, etc.],
Phosphorus compounds [e.g. tris (2,4-di-t-butylphenyl) phosphite], sulfur compounds [e.g. pentaerystyl-tetrakis (3-laurylthiopropionate), dilauryl-3,3'- Thiodipropionate, etc.]; UV absorbers {benzotriazole compounds [eg, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2-
(5-methyl-2-hydroxyphenyl) benzotriazole and the like]; light stabilizers {hindered amine compounds [for example (bis-2,2,6,6-tetramethyl-
4-piperidyl) sebacate, etc.]; adsorbents (alumina, silica gel, molecular sieve, etc.); organic or inorganic fillers; pigments; dyes; fragrances and the like. The amount of these additives to be added is usually 5% by weight or less, preferably 3% by weight, based on the weight of the hot melt adhesive, for the antioxidant, the ultraviolet absorber and the light stabilizer.
% By weight, usually 40% by weight or less for adsorbents and fillers, preferably 15% by weight or less, and usually 2% by weight or less, preferably 1% by weight or less for pigments, dyes and fragrances.

The rubber (B) constituting the hot melt adhesive of the present invention is, for example, a diene (co) polymer (a (co) polymer having a monomer composed of a diene having 4 to 18 carbon atoms as a constitutional unit). And hydrogenated products thereof, ethylene-α-olefin copolymers and the like. Specific examples of the diene (co) polymer include butadiene rubber, isoprene rubber, natural rubber, butyl rubber, nitrile rubber, styrene-
Butadiene block copolymer rubber (SBS), styrene-
Isoprene block copolymer rubber (SIS), styrene-
Butadiene random copolymer rubber (SBR), a hydrogenated product obtained by hydrogenating a part or all of the diene part of a diene (co) polymer rubber [styrene- (ethylene-propylene)]
Block copolymer rubber (SEPS; hydrogenated form of SBS),
Styrene- (ethylene-butene) block copolymer rubber (SEBS; hydrogenated form of SIS), hydrogenated SBR, etc.]
And so on.

Specific examples of the ethylene-α-olefin copolymer include a copolymer rubber of ethylene and an α-olefin (eg, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene), ethylene and α. Examples include terpolymer rubbers of olefins and non-conjugated dienes. Of these, preferred are diene (co) polymers and hydrogenated products thereof, and particularly preferred are SBS and SI.
S, SEPS and SEBS.

The melt index of the rubber (B) according to the ASTM D1238-G method (200 ° C., 5,000 g) is preferably 0.1 to 300, more preferably 0.5 to.
100. By setting the melt index of (B) within the above range, a hot melt adhesive having a good balance between cohesive force and adhesive workability (melt viscosity) can be obtained.

Examples of the tackifying resin (C) constituting the hot melt adhesive of the present invention include rosin / rosin derivative resins (eg, polymerized rosin, rosin ester, etc.), terpene resins [eg, α-pinene, β-pinene, limonene, etc. (Co) polymer], coumarone-indene resin, petroleum resin [eg C5 fraction, C9 fraction, C5 / C9 fraction, (co) polymer such as dicyclopentadiene], styrene resin [eg styrene, (Co) polymers such as α-methylstyrene and vinyltoluene having a Tg of 40 ° C. or higher], xylene resins (eg xylene formaldehyde resins), phenol resins (eg phenol xylene formaldehyde resins) and these resins And one or more resins selected from hydrogenated products thereof. Among these, preferred are terpene resin hydrogenated products and petroleum resin hydrogenated products from the viewpoint of thermal stability, odor and hue, and particularly preferred are C9 fraction and C5 / C9.
It is a hydrogenated form of a (co) polymerized petroleum resin of a fraction.

The number average molecular weight (Mn) of the tackifying resin (C) measured by GPC is preferably 200 to 3,000, more preferably 300 to 800, and the softening point by the ring and ball method is preferably 80 to 150 ° C. Preferably 100-
It is 140 ° C.

As the plasticizer (D) constituting the hot melt adhesive of the present invention, paraffin-based, naphthene-based or aromatic-based process oils; liquid resins such as liquid polybutene, liquid polybutadiene and liquid polyisoprene (M
w = 300-6000); hydrogenated products of these liquid resins; natural or synthetic wax [paraffin wax,
Microcrystalline wax, low molecular weight polyolefin (olefin has 2 to 10 carbon atoms) wax (Mw =
1,000-30,000), etc.]; and these two
Mixtures of more than one species are mentioned. Among these, preferred are paraffinic process oils, naphthenic process oils, and combinations thereof, from the viewpoint of obtaining a composition having excellent thermal stability and weather resistance.

The content of the additive containing (A) in the adhesive of the present invention is from the viewpoint of compatibility and cohesive force, the additives of the present invention, (B), (C) and (D). It is preferably from 5 to 40% by weight, more preferably from 10 to 30% by weight, based on the total weight of). Further, the content of (B) is the additive of the present invention, (B), from the viewpoint of cohesive force and processability.
It is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the total weight of (C) and (D). In addition, the content of (C) is preferably 10 to 70% by weight, and more preferably from the viewpoint of adhesiveness, based on the total weight of the additives of the present invention, (B), (C) and (D). Is 20 to 60% by weight. The content of (D) is the additive of the present invention from the viewpoint of cohesive force and adhesiveness.
Based on the total weight of (B), (C) and (D), it is preferably 0.5-35% by weight, more preferably 1-3.
It is 0% by weight.

The hot melt adhesive of the present invention may further contain the same additives as those exemplified as the optional components which can be contained in the above additives, if necessary. The content of the antioxidant, the ultraviolet absorber and the light stabilizer is usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the hot melt adhesive. The content of the adsorbent and the filler is usually 40% by weight or less, preferably 15% by weight, based on the weight of the hot melt adhesive.
It is the following. The amount of the pigment, dye and fragrance compounded is usually 2% by weight or less, preferably 1% by weight or less, based on the weight of the hot melt adhesive.

The method for producing the hot melt adhesive of the present invention is not particularly limited, and examples thereof include (A), (B),
A method of heating and melting and mixing (C) and (D); a method of adding an organic solvent (toluene, xylene, etc.) to heat and dissolve each component, uniformly mixing, and then distilling off the solvent can be used. The method is industrially preferable. As the mixing device, a heating and melting kneader can be used. The heating and melting kneader is not particularly limited in its mode shape and the like, but for example, a mixer having a screw or a ribbon-shaped stirrer having a highly compressible shape, a kneader, a single or multi-screw extruder, a mixer, etc. Can be mentioned. Mixing temperature is usually 80-200
It is preferably carried out in an atmosphere of an inert gas such as nitrogen gas in order to prevent resin deterioration.

The hot melt adhesive of the present invention has an adhesive strength,
Due to its excellent cohesive strength, plasticizer retention and processability, it can be used for a wide range of adherends (eg various plastic molded products, rubber, paper,
Cloth, metal, wood, glass, mortar concrete, etc.)
However, it is particularly suitable as a hot-melt adhesive for adhering polyolefin (polyethylene, polypropylene, etc.) resin molded products which are difficult to adhere to each other or these and other adherends mentioned above, and examples of such adhesion Examples of the method include bonding a polyolefin nonwoven fabric forming a disposable diaper and a polyolefin film.

Examples of the method for applying the hot melt adhesive of the present invention to an adherend include spiral coating, bead coating, roll coating and slot coating, but the method is not limited thereto. is not. When applied to an adherend, the melting temperature is usually 100 to 200 ° C, and the melt viscosity is usually 1 to 500 Pa · s, preferably 2 to 100 Pa · s.

The adhesive of the present invention can be used not only as a hot melt type, but also in the form of an organic solvent solution, emulsion, dispersion, film and the like. Further, the additive for improving compatibility / plasticizer retention for adhesives of the present invention is useful as a compatibilizer for various formulations, and also for moldability and resin physical properties of various thermoplastic resins or thermosetting resins. Can also be used as a modifier for asphalt, a fluidity modifier for asphalt, and the like.

[0033]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, "parts" and the numerical values in Table 1 indicate parts by weight. Production Example 1 Add 750 parts of xylene to a pressure reactor made of stainless steel,
After replacing the inside of the container with nitrogen, the temperature was raised to 180 ° C. in a sealed state. At this temperature, 500 parts of styrene, 250 parts of dicyclopentadiene, 250 parts of butyl acrylate, 1000 parts of paraffinic oil [Diana Process Oil PW-90; manufactured by Idemitsu Kosan Co., Ltd.] and 2.5 parts of di-t-butyl peroxide. The mixed solution of was added dropwise over 4 hours, and further maintained at 180 ° C. for 1 hour to complete the polymerization. The end point of the reaction was confirmed by the disappearance of the monomer by gas chromatography. Then, xylene was distilled off from the produced polymer solution (150 ° C., 2 kPa) to obtain a mixture of the copolymer (A-1) and paraffin oil. On the other hand, the Tg by the DSC method of (A-1) obtained in the same manner as above except that paraffinic oil [Diana Process Oil PW-90] was not used was −10 ° C. Number average molecular weight by GPC method is 5,500, SP of (A-1)
The value was 8.8.

Production Example 2 In Production Example 1, 500 parts of styrene as a monomer,
A mixture of the copolymer (A-2) and paraffin oil was obtained in the same manner as in Production Example 1 except that 250 parts of dicyclopentadiene and 250 parts of stearyl methacrylate were used. On the other hand, the Tg according to the DSC method of (A-2) obtained in the same manner as in Production Example 1 except that paraffinic oil [Diana Process Oil PW-90] was not used was -20 ° C. The number average molecular weight by the GPC method in (4) was 6,500, and the SP value of the (A-2) was 8.6.

Production Example 3 In Production Example 1, 650 parts of styrene as a monomer,
A mixture of the copolymer (A-3) and paraffin oil was obtained in the same manner as in Production Example 1 except that 200 parts of dicyclopentadiene and 150 parts of stearyl methacrylate were used. On the other hand, Tg by the DSC method of (A-3) obtained in the same manner as in Production Example 1 except that paraffinic oil [Diana Process Oil PW-90] was not used was -15 ° C. The number average molecular weight by the GPC method of) was 6,000, and the SP value of the (A-3) was 8.8.

Production Example 4 In Production Example 1, 300 parts of styrene as a monomer,
A mixture of the copolymer (A-4) and paraffin oil was obtained in the same manner as in Production Example 1 except that 400 parts of dicyclopentadiene and 300 parts of stearyl methacrylate were used. On the other hand, the Tg by the DSC method of (A-4) obtained in the same manner as in Production Example 1 except that paraffinic oil [Diana Process Oil PW-90] was not used was -30 ° C. The number average molecular weight by the GPC method of) was 7,000, and the SP value of the (A-4) was 8.5.

Examples 1 to 6 and Comparative Examples 1 and 2 A heating and melting kneader having a diameter of 1 inch and L / D = 10 and having a heating medium temperature of 160 ° C. capable of continuous mixing (KRC S1 manufactured by Kurimoto Tekko Co., Ltd.). ]) Was used to supply the mixture of the respective components mixed in the ratios shown in Table 1 from the raw material supply port of the heating and melting kneader to obtain the adhesive of the present invention and a comparative adhesive.

[0038]

[Table 1]

[0039] (Explanation of symbols) SBS: "Clayton D-1155" manufactured by Shell Chemical Co., Ltd.               Styrene content 40%; MI = 14 SEPS: "Septon 2043" made by Kuraray Co., Ltd.               Styrene content 13%; MI = 5 C9: partially hydrogenated petroleum resin (C9 fraction copolymer main component)               "Arcon M-115" manufactured by Arakawa Chemical Co., Ltd .; Softening point = 115 ° C C5 / C9: Hydrogenated petroleum resin (C5 / C9 distillate copolymer main component)               "Imarve P-130" manufactured by Idemitsu Petrochemical Co., Ltd.                 Softening point = 130 ℃ OIL-1: naphthenic oil "Diana Process Oil NP-24"               Made by Idemitsu Kosan Co., Ltd. OIL-2: Paraffin oil "Diana Process Oil PW-90"               Made by Idemitsu Kosan Co., Ltd. Antioxidant 1: Hindered Phenolic Antioxidant "Irganox 1010"               Ciba Specialty Chemicals Co., Ltd. Antioxidant 2: Phosphorus antioxidant "Adeka Stub 2112"               Asahi Denka Kogyo Co., Ltd. UV absorber: Benzotriazole UV absorber "Tinuvin 328"               Ciba Specialty Chemicals Co., Ltd.

Performance Test Examples The hot melt adhesives obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated for T-type peel adhesive strength, holding power, oil holding property and workability by the following test methods. .
The results are shown in Table 2. As is clear from the results in Table 2, the hot melt adhesive of the present invention has a remarkably excellent balance of T-type peel adhesive strength, holding power, oil holding property and processability as compared with the comparative example. I understand.

Test Method (T-type Peeling Adhesive Strength) Each hot melt adhesive was made to have a length of 10
0 mm x 25 mm wide x 100 μm thick polypropylene non-woven fabric applied in a bead shape with a width of 25 mm (application temperature 150
℃, coating amount 0.06g / m), polypropylene non-woven fabric of the same size or length 100mm × width 25mm × thickness 20μm polyethylene film is laminated and left for 24 hours at 25 ℃ atmosphere, using an autograph Three
The peel strength was measured at a tensile speed of 00 mm / min, and the MAX value was defined as the T-type peel adhesive strength (unit: g / 25 mm).

(Holding power) A test piece was prepared by cutting a film sheet having a thickness of 50 μm and a hot melt adhesive having a thickness of 40 μm applied thereto and cutting it into a length of 100 mm × 25 mm. A part of this test piece was peeled off into a T-shape, a weight of 100 g was hung in an atmosphere of 50 ° C., the peeled position was recorded after 60 minutes, and the peeled distance was measured (unit: mm).

(Oil Retaining Property) Each hot melt adhesive was applied to a filter paper, a load of 0.5 kg / cm ² was applied, and the temperature was 50 ° C.
After holding for 24 hours and 120 hours, the presence or absence of oil exudation on the filter paper was visually determined. Evaluation Criteria ○: No bleeding, Δ: Slight bleeding, ×: With bleeding (workability) The melt viscosity of each hot melt adhesive at 160 ° C. was measured using a BH type viscometer (unit Pa.
s).

[0044]

[Table 2]

(Explanation of symbols) PE: polyethylene film NW: polypropylene non-woven fabric

[0046]

EFFECT OF THE INVENTION The hot-melt adhesive using the additive for improving compatibility / plasticizer retention for the adhesive of the present invention has the following effects as compared with the conventional one. (1) Since the compatibility of the rubber with the tackifying resin and the plasticizer is improved, the cohesive force and the holding force are good, and the excellent adhesion to various adherends in a wide range is exhibited. In particular, it has extremely good adhesive strength to difficult-to-bond materials such as polyolefin materials. (2) The retention of the plasticizer is good, and there is almost no seepage to the adherend with time. Because of the above effects, the hot melt adhesive of the present invention is extremely useful as a hot melt adhesive or pressure sensitive adhesive for various plastics, particularly polyolefin resin molded products.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09J 153/02 C09J 153/02 191/06 191/06 (56) Reference JP-A-11-246837 (JP, A) JP 2001-187874 (JP, A) JP 63-213586 (JP, A) JP 9-78048 (JP, A) JP 9-48959 (JP, A) JP 8-109361 (JP, A) JP-A-8-3525 (JP, A) JP-A-59-182872 (JP, A) JP-A-62-192441 (JP, A) JP-A-2000-26824 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C09J 4/00-201/10

Claims (8)

(57) [Claims] 1. An additive for an adhesive comprising a rubber, a tackifying resin and a plasticizer, wherein the styrene monomer (a1) is selected from the group consisting of styrene, α-methylstyrene and a styrene derivative, and has 4 to 20 carbon atoms. An aliphatic or alicyclic unsaturated hydrocarbon (a2) and an alkyl or alkenyl (meth) acrylate (a3) having 4 to 24 carbon atoms in the alkyl or alkenyl group are essential constituent monomers, and (a1), ( a2) and (a3)
(A1) is 25 ≦ (a1) <75% by weight based on the weight of the copolymer (A) in which
2) is 15 ≦ (a2) <65% by weight, (a3) is 10 <
(A3) ≦ 60% by weight and number average molecular weight is 500
To 10,000, a glass transition temperature (Tg) of 20 ° C. or lower, and a solubility parameter (SP value) of 7.5 to 9.5, which is a copolymer (A). Additives to improve and improve plasticizer retention. 2. The weight of the monomer constituting (A) is
Based on the weight of (A), (a1) is 30 ≦ (a1) ≦
65% by weight, (a2) is 20 ≦ (a2) ≦ 55% by weight,
The additive according to claim 1, wherein (a3) is 15 ≦ (a3) ≦ 50% by weight, and the other monomer (a4) is 0 or 0.1 ≦ (a4) ≦ 10% by weight. 3. The additive according to claim 1, wherein (A) is polymerized by a coexisting polymerization method. 4. The additive according to claim 1, at least one rubber (B) selected from a diene (co) polymer and an ethylene-α-olefin copolymer, a tackifying resin (C), and Comprises a plasticizer (D), (A),
5-40% by weight of the additive, 5-40% by weight of (B), based on the total weight of (B), (C) and (D),
10 to 70% by weight of (C) and 0.5 to 35 of (D)
Hot melt adhesive which is wt%. 5. The rubber (B) has a styrene unit content of 30.
~ 55 wt% styrene-butadiene block copolymer, styrene-isoprene block copolymer and /
The hot melt adhesive according to claim 4, which is a hydrogenated product thereof. 6. The hot melt adhesive according to claim 4, wherein the plasticizer is a plasticizer selected from the following (1) to (5). (1) Paraffin-based, naphthene-based or aromatic-based process oil (2) Liquid resin selected from liquid polybutene, liquid polybutadiene and liquid polyisoprene (3) Hydrogenated product (4) of the above (1) and (2) Natural or synthetic wax (5) Mixture of two or more of the above (1) to (4) 7. The method according to claim 4, which is used for a plastic molded product.
~ 6 hot melt adhesives in any one. 8. An adhesive body obtained by adhering the polyolefin resin molded articles or the adherend to each other with the hot melt adhesive according to any one of claims 4 to 7.