JP2005105205A - Hotmelt adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hotmelt adhesive having a good touch feeling of the adhered material, excellent in cohesive force and a balance of its sticking adhesive force with various adhered material such as a polyolefin-based resin, etc., and coating property. <P>SOLUTION: This hot melt adhesive consists of (A) a rubber selected from a diene (co)polymer such as a styrene-butadiene block copolymer, an ethylene-isoprene block copolymer, their hydrogenated materials, etc., and an ethylene-α-olefine copolymer, (B) an adhesiveness-imparting resin and (C) a plasticizer is provided with that the (A) contains 2 kinds of (a-1) a linear type rubber and (a-2) a radiation type rubber as indispensable components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hot melt adhesive. More specifically, the present invention relates to a hot melt adhesive that is particularly suitable for bonding polyolefin-based resin molded products, has flexibility that does not impair the texture of the resin molded products, and has excellent cohesive strength.

Conventionally, as hot melt adhesives used for bonding polyolefin films, nonwoven fabrics, resin molded products, etc., styrene-ethylene-propylene-styrene block copolymer rubber or styrene-butadiene-styrene block copolymer rubber is tackified. Liquid plasticizers such as resin components and process oils, and other additives are known (for example, Patent Documents 1 and 2).
JP-A-8-60121 Japanese Patent No. 3038549

  However, when the above is used as a hot-melt adhesive, if the open time (the time until bonding after application is possible) is increased or the melt viscosity is reduced, the cohesive strength and holding power are increased. This causes a problem such as a decrease in adhesion to an adherend such as an olefin-based resin molded product, and an increase in cohesion causes a problem that flexibility decreases and the texture of the resin molded product is impaired. It was.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve these problems and obtain an adhesive having excellent adhesive strength and cohesive strength and excellent flexibility.
That is, the present invention relates to a hot melt adhesive comprising a rubber (A) selected from a diene (co) polymer and an ethylene-α-olefin copolymer, a tackifier resin (B), and a plasticizer (C). Is a hot melt adhesive characterized in that it contains two types of essential components, linear type rubber (a-1) and radial type (a-2).

The hot melt adhesive of the present invention has the following effects compared to the conventional one.
(1) Since the hot melt adhesive is soft, it has an excellent texture of the bonded body, and has good cohesion and holding power, and therefore has excellent adhesion to various adherends. In particular, the adhesive strength to difficult-to-bond materials such as polyolefin-based materials is extremely good. Furthermore, since it has a low melt viscosity and can be applied at a low temperature, it can be directly applied to an adherend such as a polyethylene film having low heat resistance.
(2) Since the heat loss of the hot melt adhesive is low, generation of mist at the time of melting is suppressed, and generation of odor is extremely small.

The rubber (A) constituting the hot melt adhesive of the present invention is a rubber selected from a diene (co) polymer and an ethylene-α-olefin copolymer.
The diene (co) polymer includes a monomer having 4 to 18 carbon atoms (for example, butadiene, isoprene, etc.) or other monomer (diene to other monomer in a weight ratio of 0.1). (Co) polymer having a structural unit of ˜100: 0 to 99.9) and a hydrogenated product thereof. Other monomers include aromatic vinyl monomers (preferably having 8 to 20 carbon atoms such as α-methylstyrene and styrene), olefins (preferably having 2 to 8 carbon atoms such as ethylene and propylene), Unsaturated nitriles (preferably having 32 to 16 carbon atoms, such as acrylonitrile) are included.
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), hydrogenated hydrogenated part of diene part of diene (co) polymer rubber [styrene- (ethylene-propylene) block copolymer rubber (SEPS; hydrogenation of SIS) Body), styrene- (ethylene-butene) block copolymer rubber (SEBS; hydrogenated SBS), hydrogenated SBR, etc.].

As the ethylene-α olefin copolymer, a copolymer rubber (ethylene and α) of ethylene and an α olefin (3 to 18 carbon atoms: propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, etc.) is used. Olefin weight ratio 0.1 to 95: 5 to 99.9), terpolymer rubber (ethylene) of ethylene, α-olefin and non-conjugated diene (4 to 18 carbon atoms: eg ethylidene norbornene, dicyclopentadiene, etc.) And α-olefin and non-conjugated diene in a weight ratio of 30 to 90: 5 to 80: 0.1 to 30).
Among (A), preferred are a diene (co) polymer and a hydrogenated product thereof, and particularly preferred are SBS, SIS, SEPS, and SEBS, and a mixture of two or more thereof.

The number average molecular weight of (A) is preferably 10,000 to 400,000, more preferably 30,000 to 300,000. By setting the number average molecular weight of (A) within the above range, a hot melt adhesive having a good balance between cohesive force and melt viscosity can be obtained. Cohesive force is a factor affecting adhesive strength, and melt viscosity is a factor affecting adhesive processability.
Moreover, the melt index by ASTMD1238-G method (200 ° C., 5,000 g) of (A) is preferably 300 or less, more preferably 100 or less. By setting the melt index of (A) within the above range, a hot melt adhesive having a good balance between cohesive force and melt viscosity can be obtained.

  (A) which comprises the hot-melt-adhesive of this invention has said composition, and contains 2 types of linear type rubber (a-1) and radial type rubber (a-2) as an essential component. The linear rubber (a-1) refers to a rubber having no branch point in the molecular chain and two so-called end groups. The branching point means a point where the branch is in contact with the molecular chain, and the branch is an oligomer or a high molecular weight branch extending from the molecular chain, and its property is greatly changed by removal. The radial rubber (a-2) is a rubber having three or more so-called end groups having at least one branch point in the molecular chain. Radial type rubbers include those having molecular chains of star shape, comb shape, and the like.

(A-1) is preferably a linear diene (co) polymer, more preferably the content (% by weight) of the other monomer in the linear diene (co) polymer is ( Based on the weight of a-1), it is 25 to 65%, particularly preferably 30 to 60%, and most preferably 35 to 55%. When the content of the other monomer is 25% by weight or more, the cohesive strength of the obtained hot melt adhesive does not decrease, and when it is 65% by weight or less, the adhesive does not become too hard and the texture of the bonded body is good. Adhesiveness does not decrease.
(A-2) is preferably a radial diene (co) polymer, more preferably the content (% by weight) of the other monomer in the radial diene (co) polymer is that of (a-2). Based on the weight, it is 5 to 40%, particularly preferably 10 to 35%, most preferably 15 to 30%. When the content of the other monomer is 5% by weight or more, the cohesive strength of the obtained hot melt adhesive does not decrease, and when it is 40% by weight or less, the adhesive does not become too hard and the texture of the bonded body is good. Adhesiveness does not decrease.
The ratio (weight ratio) between (a-1) and (a-2) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and particularly preferably 30:70 to 70:30. It is. By using the above ratio, a hot cohesive with a high cohesion and flexibility can be obtained.

As the tackifier resin (B), known resins {for example, described in Adhesion Technology 20, (2), 13 (2000)} and the like can be used, and specific examples thereof include, for example, rosin, rosin derivative resin [for example, , Polymerized rosin, rosin ester, etc .: number average molecular weight (hereinafter referred to as Mn) 200 to 1,000], terpene resin [for example, (co) polymers such as α-pinene, β-pinene, limonene, and their phenol modifications Bodies: Mn300-1200], coumarone-indene resin (Mn300-1200), petroleum resin [for example, (co) polymers such as C5 fraction, C9 fraction, C5 / C9 fraction, dicyclopentadiene, etc. Mn300 to 1200], styrene resin [for example, (co) polymer such as styrene, α-methylstyrene, vinyltoluene, etc., with Mn of 200 to 1,000 and Tg of 40 ° C. or higher], xylene resin (for example, Xylene formaldehyde resin and the like: Mn 300 to 3,000), phenolic resins (for example, phenol xylene formaldehyde resin and the like: Mn 300 to 3,000) and one or more resins selected from hydrogenated products of these resins. .
Among these, preferred are hydrogen bodies such as hydrogenated terpene resins and hydrogenated petroleum resins from the viewpoint of thermal stability, odor and hue, and particularly preferred are C9 fraction, C5 / C9. A hydrogenated product of a (co) polymerized petroleum resin of a fraction and a hydrogenated product of a (cyclo) diene-based (co) polymerized petroleum resin.
The Mn and the weight average molecular weight (hereinafter referred to as Mw) described above and below are values obtained by gel permeation chromatography (GPC) using polystyrene as a standard. Tg is the glass transition point.

As the plasticizer (C), known plasticizers {for example, described in Adhesion Technology 20, (2), 21 (2000)} can be used, and specific examples thereof include, for example, paraffinic, naphthenic, or aromatic Group process oils; liquid polybutene, liquid polybutadiene, liquid polyisoprene, and other resins that are liquid at room temperature (Mw = 300 to 10,000); hydrogenated products of these liquid resins; natural or synthetic waxes [paraffins] Wax, microcrystalline wax, low molecular weight polyolefin wax (Mw = 1,000 to 30,000), etc.]; and mixtures of two or more thereof.
Among these, paraffinic process oil, naphthenic process oil, and combinations thereof are preferable from the viewpoint of obtaining a composition excellent in thermal stability and weather resistance.

  In the hot melt adhesive of the present invention, the loss on heating after 3 hours in an air atmosphere at 150 ° C. is preferably 0.01 to 2.00% by weight, more preferably 0.05 to 1.90% by weight, Especially preferably, it is 0.10 to 1.80 weight%. That is, the loss on heating (% by weight) is preferably 0.01 or more, more preferably 0.05 or more, and particularly preferably 0.10 or more. Moreover, 2.00 or less is preferable, More preferably, it is 1.90 or less, Most preferably, it is 1.80 or less. If the weight loss by heating is 0.01% by weight or more, there is a tendency that a low molecular weight component is not insufficient and sufficient adhesiveness is obtained. If the weight loss is 2.00% by weight or less, the volatile components do not increase and odor is generated when melted And mist tend not to occur, and adhesion does not decrease.

(Measurement method of heat loss)
An aluminum dish having a diameter of 50 mm and a depth of 20 mm is precisely weighed (the weight of the aluminum dish is W ₁ g). About 2 g of the adhesive sample is precisely weighed and weighed on an aluminum pan (the weight of the sample is W ₂ g). The aluminum dish containing the sample is placed in an air atmosphere in a 150 ° C. circulating air dryer [for example, SPHH200 type safety oven; manufactured by Tabai Espec Co., Ltd.]. After leaving it to stand for 3 hours, it is taken out and cooled in a desiccator for 30 minutes, and then the weight is accurately weighed (weight is defined as W ₃ g). Heat loss can be obtained from the following equation.
Loss on heating (%) = 100 {(W ₁ + W ₂ ) −W ₃ } / W ₂

The adhesive of the present invention comprises the above (A) to (C), but may further contain the following copolymer (D).
(D) is a copolymer having the following (i), (ii) and / or (iii) as constituent monomers.
(i) Aromatic vinyl monomer (d-1)
(ii) C4-C20 (preferably C4-16) aliphatic or alicyclic monounsaturated hydrocarbon (d-2)
(iii) alkyl or alkenyl (meth) acrylate (d-3) having 4 to 24 carbon atoms in the alkyl or alkenyl group

  Examples of the aromatic vinyl monomer (d-1) include styrene, α-methylstyrene, and styrene derivatives [for example, alkylstyrene having 1 to 4 or more carbon atoms in an alkyl group (vinyltoluene, ethylstyrene, t-butylstyrene, etc.) , Halogenated styrene (for example, chlorostyrene, bromostyrene, fluorostyrene and the like), amino group-containing styrene (for example, N, N-diethylaminostyrene and the like) and the like. These can also be used as a mixture of two or more. Of these, α-methylstyrene and styrene are preferable, and styrene is more preferable.

  Specific examples of aliphatic or alicyclic monounsaturated hydrocarbons (d-2) having 4 to 20 carbon atoms (preferably 4 to 16 carbon atoms) include aliphatic monounsaturated hydrocarbons [monoolefins such as 1-butene , 4-methyl-1-pentene, 1-pentene, 2-pentene, 1-octene, 1-decene, 1-dodecene, etc.); alicyclic monounsaturated hydrocarbons (eg cyclopentene, methylcyclopentene, etc.); and these The mixture of 2 or more types of these is mentioned. Of these, more preferred are aliphatic monounsaturated hydrocarbons having 4 to 12 carbon atoms and alicyclic monounsaturated hydrocarbons having 5 to 14 carbon atoms, and particularly preferred are 1-butene and cyclopentene.

  Specific examples of the alkyl or alkenyl (meth) acrylate (d-3) having 4 to 24 carbon atoms in the alkyl or alkenyl group include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Examples include myristyl (meth) acrylate, stearyl (meth) acrylate, and oleyl (meth) acrylate. These can also be used as a mixture of two or more. Of these, preferred are alkyl (meth) acrylates having 12 to 18 carbon atoms in the alkyl group, and more preferred is stearyl (meth) acrylate.

The copolymer (D) has other monomer (d-4) as necessary in addition to the above (d-1) and (d-2) and / or (d-3) as a constituent monomer. It may be.
Specific examples of (d-4) include hydroxyl group-containing (meth) acrylate [(meth) acrylate having 4 to 10 carbon atoms of hydroxyalkanol, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, polyoxyalkylene (2 to 4 carbon atoms) glycol (polymerization degree 2 to 10 or more) mono (meth) acrylate, etc.]; amino group-containing (meth) acrylate [dialkyl (1 to 10 carbon atoms) amino Alkyl (2 to 10 carbon atoms) (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.]; unsaturated carboxylic acids [3 to 22 carbon atoms, monocarboxylic acid such as (meth) Acrylic acid, (iso) crotonic acid and cinnamic acid, dicarboxylic acid For example, (maleic anhydride), fumaric acid, (anhydrous) itaconic acid, monoalkyl (1 to 20 carbon atoms) esters of these dicarboxylic acids, etc .; (meth) acrylates other than the above (d3) [for example, alkyl group C1-C3 alkyl (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate etc.], alicyclic (di) cycloalkyl (meth) acrylate [C8- 16, for example, cyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, etc.], aralkyl (meth) acrylate [carbon number 9 to 21, such as benzyl (meth) acrylate, etc.], etc .; epoxy group-containing (meth) acrylate [carbon 2 to 18, such as glycidyl (meth) acrylate]; Dialkyl (carbon number 1 to 20) ester of saturated dicarboxylic acid [carbon number 6 to 44, for example, diethyl malate, dibutyl fumarate, etc.]; Amide group or imide group-containing monomer, for example, imidized product of the above unsaturated dicarboxylic acid [carbon 4-20, such as maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, etc.] amidated products of the above unsaturated monocarboxylic acids [for example, (meth) acrylamide mono- and dialkyl (carbon number 1-10) ) Aminoalkyl (2 to 10 carbon atoms) (meth) acrylamide]; polyfunctional aromatic vinyl monomer (for example, divinylbenzene); polyfunctional (meth) acrylate monomer [two (meth) acryloyl groups in one molecule A compound having, for example, di (meth) acrylate of neopentyl glycol A compound having three or more (meth) acryloyl groups in one molecule [for example, tri (meth) acrylate of trimethylolpropane, tri- or tetra- (meth) acrylate of pentaerythritol, etc.]]; A mixture of two or more of these may be used.
Among these, preferred are unsaturated carboxylic acids, (meth) acrylates having 1 to 3 carbon atoms in the alkyl group, and dialkyl esters of unsaturated dicarboxylic acids, and more preferred are (meth) acrylic acid, maleic anhydride, Ethyl methacrylate and dialkyl maleate (C1-20) ester.

The content of (d-1) constituting the copolymer (D) is preferably 25 to 85% by weight, more preferably 35 to 75%, based on the weight of (D), from the viewpoints of cohesive strength and flexibility. % By weight. That is, the content (% by weight) of (d1) is preferably 25 or more, more preferably 35 or more. Moreover, 85 or less is preferable, More preferably, it is 75 or less.
(D-2) Each content of (d-3) is preferably 15 to 75% by weight, more preferably 25 to 65%, based on the weight of (D), from the viewpoints of cohesive strength and plasticizer retention. % By weight. That is, the content (% by weight) of (d2) is preferably 15 or more, more preferably 25 or more. Moreover, 75 or less is preferable, More preferably, it is 65 or less.
When other monomer (d-4) is used, the content of (d-4) is preferably 0.01 to 10% by weight, more preferably 0.8%, from the viewpoint of compatibility with rubber (A) and the like. 1 to 5% by weight.

The copolymer (D) can be obtained by polymerizing the above-described constituent monomers by a known method such as radical polymerization, thermal polymerization, or cationic polymerization. The resulting polymer includes random, block and graft polymers.
Although a manufacturing method is not specifically limited, For example, the following radical polymerization method can be illustrated.
(1) A monomer is continuously or intermittently supplied into a heated solvent in the presence of a polymerization initiator, and after completion of the polymerization, the solvent and, if necessary, unreacted monomers are distilled off at normal pressure or reduced pressure to co-polymerize. A method for obtaining a coalescence (solution polymerization method).
Solvents used for solution polymerization include aromatic hydrocarbons (toluene, xylene, cumene, etc.), aliphatic hydrocarbons (n-hexane, n-octane, n-decane, etc.), alicyclic hydrocarbons (cyclohexane, Methyl cyclohexane, halogen-containing systems (chloroform, carbon tetrachloride, dichloroethane, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (dioxane, dibenzyl ether, etc.), esters (ethyl acetate, isopropyl acetate, butyl acetate) ) And the like.
(2) A polymerization initiator is added to a solution obtained by dissolving the monomer alone or a copolymer obtained by polymerizing in advance in the monomer, and after heating and polymerizing, the unreacted monomer is removed under normal pressure or reduced pressure as necessary. A method of obtaining a copolymer by distilling off (bulk polymerization method).

(3) In one or more melts selected from the group that may optionally contain (A), (B), (C) and (E) described later, which are constituents of a hot melt adhesive, or the melt In the solution obtained by adding the above solvent to the product, in the presence of a polymerization initiator, the monomer is continuously or intermittently supplied for polymerization, and after completion of the polymerization, the solvent and unreacted monomer are removed at normal pressure or reduced pressure as necessary. A method of distilling off to obtain a mixture comprising a copolymer and other components (coexistence polymerization method).
The polymerization temperature in the radical polymerization is preferably in the range of 80 to 240 ° C., and the type and amount of the polymerization initiator to be used can be appropriately selected according to the target molecular weight. 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 at which the solvent or unreacted monomer is distilled off varies depending on the type of monomer, but is preferably 100 to 200 ° C. Among the radical polymerization methods of the copolymer (D), the coexistence polymerization method is preferable from the viewpoint of compatibility.

As a polymerization initiator used for manufacture of a copolymer (D), the azo polymerization initiator and organic peroxide polymerization initiator which are normally used for radical polymerization are mentioned. Examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4 dimethylvaleronitrile), and 2,2′-azobis (2-methylbutyronitrile). ) And the like. As the organic peroxide-based polymerization initiator, peroxyketal [2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1bis (t-butylperoxy) cyclohexane, 1, 1-bis (t-butylperoxy) -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.), peroxyesters (t-butylperoxybenzoate, t-hexylperoxyisopropyl monocarbonate) Di-t-butylperoxy Kisa Hydro terephthalate), an organic peroxide peroxydicarbonate (di -n- propyl peroxydicarbonate, etc.). Two or more of these can be used in combination.
Among these, preferred are organic peroxide polymerization initiators, more preferred are dialkyl peroxides and peroxyesters, and particularly preferred are di-t-butyl peroxide, dicumyl peroxide and t-butyl peroxide. Benzoate.
The amount of the polymerization initiator used is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, based on the total weight of the monomers. That is, the use amount (% by weight) of the polymerization initiator is preferably 0.01 or more, more preferably 0.05 or more. Moreover, 20 or less is preferable, More preferably, 15 or less is preferable. When the amount of the polymerization initiator used is 0.01% by weight or more, the polymerization proceeds moderately, and when it is 20% by weight or less, the resulting copolymer does not have a low molecular weight and the loss on heating is reduced.

In the production of the copolymer (D), a chain transfer agent can be used as necessary to adjust the molecular weight.
Examples of chain transfer agents include α-olefins (such as 1-dodecene), mercaptans (such as t-butyl mercaptan, n-dodecyl mercaptan), disulfides (such as bis-2-amino-phenyl disulfide, diisopropyl xanthogen disulfide). Etc.), diazothioether (for example, p-methoxyphenyldiazothio-2-naphthyl ether, etc.), organic halides (for example, carbon tetrachloride, carbon tetrabromide, chloroform, etc.) and the like. Those of 01 or more are preferable.
When the chain transfer agent is used, the amount of the chain transfer agent used is preferably 10% by weight or less, more preferably 0.01 to 5% by weight, based on the total weight of the monomers. That is, the amount (% by weight) of the chain transfer agent is preferably 10 or less, more preferably 5 or less. Moreover, 0.01 or more is preferable. When the amount of the chain transfer agent used is 10% by weight or less, the resulting copolymer is preferably reduced in heat loss.

  The Tg of the copolymer (D) is preferably −50 ° C. or higher, more preferably −40 ° C. or higher from the viewpoint of improving the cohesive strength of the adhesive obtained by blending (D). And from a viewpoint of softening the adhesive obtained by mix | blending (D) and improving the adhesive force in low temperature, 20 degrees C or less is preferable, More preferably, it is 0 degrees C or less. That is, the Tg of (D) is preferably -50 to -20 ° C, more preferably -40 to 0 ° C.

  The number average molecular weight (Mn) of the copolymer (D) is preferably 500 or more, more preferably 1,000 or more, from the viewpoint of improving the cohesive force and holding force of the adhesive. Moreover, 10,000 or less is preferable from a viewpoint of improving compatibility with rubber | gum (A) and improving adhesive force, More preferably, it is 5,000 or less. That is, the Mn of (D) is preferably 500 to 10,000, more preferably 1,000 to 5,000. Moreover, the weight average molecular weight (Mw) of a copolymer (D) becomes like this. Preferably it is 1,000-20,000, More preferably, it is 1,500-10,000. That is, the Mw of (D) is preferably 1,000 or more, more preferably 1,500 or more. Moreover, 20,000 or less is preferable, More preferably, it is 10,000 or less. The ratio of Mw to Mn (Mw / Mn) is preferably 1.2 to 2.5, more preferably 1.3 to 2.0. That is, Mw / Mn is preferably 1.2 or more, more preferably 1.3 or more. Moreover, 2.5 or less is preferable, More preferably, it is 2.0 or less.

The solubility parameter (hereinafter referred to as SP value) of the copolymer (D) improves the compatibility with the rubber (A) and the plasticizer (C), improves the adhesive force, and improves the plasticizer retention. Therefore, 7.5 to 11.5 is preferable, more preferably 7.8 to 11.2, and particularly preferably 8.0 to 11.0. That is, 7.5 or more is preferable, More preferably, it is 7.8 or more, Most preferably, it is 8.0 or more. Moreover, 11.5 or less is preferable, More preferably, it is 11.2 or less, Most preferably, it is 11.0 or less.
In addition, SP value is a value calculated | required from following Formula.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ).
ΔH and V are the total heat of molar evaporation (Δe _i ) of the atomic group described in “POLYMER ENGINEERING AND FEBRUARY, 1974, Vol. 14, No. 2, ROBERTF. FEDORS. (Pages 151 to 153)”. The sum (V) of (ΔH) and the molar volume (Δv _i ) can be used.

  The hot melt adhesive of the present invention comprises a rubber (A), a tackifier resin (B), a plasticizer (C), a copolymer (D) and optionally a glass transition temperature (hereinafter referred to as Tg) higher than (D). The (co) polymer (E) having (described below) can be contained. In the above and below, Tg is a value determined by a differential scanning calorimetry (DSC) method.

Specific examples of the (co) polymer (E) include a (co) polymer (E-1) and a polycondensation polymer (E-2) having an aromatic ring-containing monomer as an essential constituent monomer. It is done. A (co) polymer is preferred.
An aromatic vinyl monomer (d-1) etc. can be used as an aromatic ring containing monomer in (E-1). Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable. As the monomer constituting the (co) polymer (E), another monomer (d-5) can be copolymerized with the above (d1) if necessary.
Specific examples of (d-5) include the above (d-2), (d-3), (d-4) and the like. Among these, preferred are unsaturated carboxylic acids, (meth) acrylates having 1 to 24 carbon atoms in the alkyl group, and dialkyl esters of unsaturated dicarboxylic acids, and more preferred are (meth) acrylic acid and alkyl (meth). Acrylate (having 12 to 18 carbon atoms).
When other monomer (d-5) is used, the amount of (d-5) constituting (E-1) is preferably 0.01 to 10 from the viewpoint of the compatibility and cohesive strength of the hot melt adhesive. % By weight, more preferably 0.1 to 5% by weight.
The production method and polymerization conditions for producing (E-1) may be the same as for producing (D).

Examples of the polycondensation polymer (E-2) include polyamide, polyimide, polyester, polycarbonate, polyphenylene oxide, polysulfone, polyphenylene sulfide, polyether ketone and modified products thereof, and polyaddition polymers (polyurethane etc.).
Examples of the polyamide include polyphenylene adipamide. Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate. Examples of the polycarbonate include polyoxycarbonyloxy-1,4-phenylene isopropylidene-1,4-phenylene. Examples of polyphenylene oxide include poly-1,4-phenylene oxide and poly-2,6-dimethyl-1,4-phenylene oxide. Examples of polysulfone include polyoxy-1,4-phenylenesulfonyl-1,4-phenylene. Examples of polyphenylene sulfide include polythio-1,4-phenylene. Examples of the polyurethane include polyphenylene hexamethylene diurethane.
Of these, polycondensation polymers are preferable, polyphenylene oxides are more preferable, and poly-2,6-dimethyl-1,4-phenylene oxide is particularly preferable.

The Tg of the (co) polymer (E) is at least 10 ° C. higher than the Tg of the copolymer (D) from the viewpoint of achieving both heat resistance and flexibility of the hot melt adhesive obtained by blending (E). More preferably, it is 15 ° C. or higher, particularly preferably 20 ° C. or higher, most preferably 40 ° C. or higher. The Tg of (E) is preferably 25 ° C. or higher, more preferably 30 ° C. or higher from the viewpoint of improving the cohesive strength of the adhesive obtained by blending (E). Further, from the viewpoint of improving the compatibility of the adhesive obtained by blending (E) and not increasing the melt viscosity of the hot melt adhesive of the present invention, it is preferably 200 ° C or lower, more preferably 180 ° C or lower. is there. That is, Tg of (E) is preferably 25 to 200 ° C, more preferably 30 to 180 ° C.
From the viewpoint of improving the cohesive strength of the adhesive, Mn of (E) is preferably 1,300 or more, more preferably 1,500 or more. Moreover, 10,000 or less are preferable from a viewpoint of improving compatibility with rubber | gum (A), More preferably, it is 5,000 or less. That is, 1,300 to 10,000 are preferable, and more preferably 1,500 to 5,000. Moreover, Mw of (E) is preferably 1,500 to 20,000, more preferably 2,000 to 10,000. That is, Mw of (E) is preferably 1,500 or more, more preferably 2,000 or more. Moreover, 20,000 or less is preferable, More preferably, it is 10,000 or less. Mw / Mn is preferably 1.2 to 3.0, more preferably 1.3 to 2.5. That is, Mw / Mn is preferably 1.2 or more, more preferably 1.3 or more. Moreover, 3.0 or less is preferable, More preferably, it is 2.5 or less.
The SP value of (E) is preferably from 8.4 to 12.0, more preferably from 8.5 to 11.8 from the viewpoint of improving compatibility with (A) and (C) and improving the adhesive force. Particularly preferably, it is 8.6 to 11.5.
That is, the SP value of (E) is preferably 8.4 or more, more preferably 8.5 or more, and particularly preferably 8.6 or more. Moreover, 12.0 or less is preferable, More preferably, it is 11.8 or less, Most preferably, it is 11.5 or less.

The content of the rubber (A) relative to the total weight of (A), (B), (C), (D) and (E) in the hot melt adhesive of the present invention is determined from the viewpoint of improving the cohesive force. Based on the total weight, it is preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 12% by weight or more. Further, from the viewpoint of melt viscosity, it is preferably 40% by weight or less, more preferably 30% by weight or less, and particularly preferably 28% by weight or less. That is, the content of (A) is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and particularly preferably 12 to 28% by weight.
The content of the tackifying resin (B) with respect to the total weight is preferably 10% by weight or more, more preferably 20% by weight or more, and particularly preferably 25% based on the total weight of the adhesive from the viewpoint of improving the adhesive strength. % By weight or more.
Moreover, from a viewpoint of improving a softness | flexibility, 70 weight% or less is preferable, More preferably, it is 60 weight% or less, Most preferably, it is 55 weight% or less. That is, the content of (B) is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and particularly preferably 30 to 55% by weight.

The content of (C) with respect to the total weight is preferably 1% by weight or more, more preferably 5% by weight or more, and particularly preferably 8% by weight or more based on the total weight of the adhesive from the viewpoint of melt viscosity. . Further, from the viewpoint of improving the cohesive force, it is preferably 30% by weight or less, more preferably 25% by weight or less, and particularly preferably 22% by weight or less. That is, the content of (C) is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, and particularly preferably 8 to 22% by weight.
The content of (D) in the adhesive is preferably 1% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% based on the total weight of the adhesive from the viewpoint of improving the compatibility of each component. % By weight or more. Further, from the viewpoint of improving the cohesive force, it is preferably 40% by weight or less, more preferably 35% by weight or less, and particularly preferably 30% by weight or less.
That is, the content of (D) is preferably 1 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably 10 to 30% by weight.
The content of (E) with respect to the total weight is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, particularly preferably 0, based on the total weight of the adhesive from the viewpoint of improving the resin strength. .8% by weight or more. From the viewpoint of improving flexibility, it is preferably 30% by weight or less, more preferably 25% by weight or less, and particularly preferably 20% by weight or less. That is, the content of (E) is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, and particularly preferably 0.8 to 20% by weight.

  The content ratio (D) / (E) between (D) and (E) is preferably 0.1 or more, more preferably from the viewpoint of compatibility and cohesive strength of each component in the hot melt adhesive. 5 or more. Moreover, 30 or less is preferable, More preferably, it is 20 or less. That is, (D) / (E) is preferably from 0.1 to 30, and more preferably from 0.5 to 20.

The hot melt adhesive of the present invention can contain other additives (F) as necessary.
As (F), an antioxidant {hindered phenol-based compound [for example, pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], phosphorus compounds [for example, tris (2,4-di-t-butylphenyl) phosphite, etc.], sulfur compounds [for example, pentaerythryl- Tetrakis (3-laurylthiopropionate), dilauryl-3,3′-thiodipropionate, etc.], etc .; UV absorber {benzotriazole compounds [eg 2- (3,5-di-t-amyl- 2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.] etc .; Fixed agent {hindered amine compound [eg (bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.] etc.]; adsorbent (eg alumina, silica gel, molecular sieve etc.); organic or inorganic filler (For example, talc, mica, calcium carbonate, etc., titanium oxide, calcium oxide, etc.); pigments; dyes;
When other additives (F) are added, the amount of these additives is 0.01 to 5% by weight of the antioxidant, ultraviolet absorber and light stabilizer based on the weight of the hot melt adhesive. Is more preferable, and 0.1 to 3% by weight is more preferable. Moreover, in an adsorbent and a filler, 0.01 to 40 weight% is preferable, More preferably, it is 0.1 to 15 weight%. Moreover, in a pigment, dye, and a fragrance | flavor, 0.005 to 2 weight% is preferable, More preferably, it is 0.01 to 1 weight%.

  Although it does not specifically limit as a manufacturing method of the hot-melt-adhesive of this invention, For example, (i) (A), (B), (C), the method of adding (D) and (E) which are added as needed, heat-melt mixing And (ii) a method in which an organic solvent (toluene, xylene, etc.) is added and each component is heated and dissolved, and after uniform mixing, the solvent is distilled off. Industrially preferred is the method (i). Moreover, a heating melt kneader can be used as the mixing device. There are no particular restrictions on the shape of the hot melt kneader, but for example, a pressure reactor with a stirrer, a mixer having a highly compressible screw or ribbon stirrer, a kneader, a uniaxial Or a multi-screw extruder, a mixer, etc. can be mentioned. The mixing temperature is usually 80 to 200 ° C., and it is preferably performed in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration.

In the hot melt adhesive of the present invention, the melt viscosity at 140 ° C. is preferably 1,000 to 10,000 mPa · s, more preferably 1,500 to 8,000 mPa · s, and particularly preferably 2, 000 to 7,000 mPa · s. When the melt viscosity at 140 ° C. is less than 1,000 mPa · s, the cohesive force of the hot melt adhesive tends to be difficult to decrease, and when it is less than 6,000 mPa · s, the coating property is good. The melt viscosity at 140 ° C. is measured by the following method.
(Measuring method of melt viscosity): A sample of about 8 g was put into a test tube having an inner diameter of 16 mm and a height of 105 mm, and the temperature was adjusted to 140 ° C. for 20 minutes in an oil bath, and an SB viscometer (JIS K7117-1987, SB4) No. spindle (for example, BL type viscometer and No. 4 rotor manufactured by Toki Sangyo Co., Ltd.) was set and the temperature was further adjusted for 10 minutes. After confirming that the sample temperature reached 140 ° C, the rotor was rotated. Rotate at several 60 rpm and read the melt viscosity after 10 minutes. Hereinafter, the melt viscosity at 140 ° C. is referred to as 140 ° C. melt viscosity.
The melt viscosity at 140 ° C. is preferably 1,000 to 10,000 mPa · s, more preferably 1,500 to 8,000 mPa · s, and particularly preferably 2,000 to 7,000 mPa · s. That is, the 140 ° C. melt viscosity (Pa · s) is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 2,000 or more. Moreover, it is preferably 6,000 or less, more preferably 5,800 or less, and particularly preferably 5,500 or less. When the melt viscosity at 140 ° C. is less than 1,000 mPa · s, the cohesive force of the hot melt adhesive tends to decrease, and when it exceeds 6,000 mPa · s, the coating property tends to decrease.

  In the hot melt adhesive of the present invention, the loss tangent loss tan δ is a physical property mainly related to the coating property, preferably tan δ at 90 ° C. is 0.1 to 53.0 under 100 Hz, and 100 Hz. The tan δ at 150 ° C. is 0.5 to 10.0, more preferably 100 Hz, the tan δ at 90 ° C. is 0.2 to 31.0, and the tan δ at 100 ° C. at 150 ° C. is 0.8 to 5.0. In some cases, the hot melt adhesive of the present invention having excellent coatability is obtained. By setting tan δ at 100 ° C. and 90 ° C. to 0.1 or more and tan δ at 100 Hz and 150 ° C. to 0.5 or more, a hot melt adhesive having appropriate plasticity and good coatability can be obtained. In addition, by setting tan δ at 100 Hz and 90 ° C. to 53.0 or less and tan δ at 100 Hz and 150 ° C. to 10.0 or less, a hot melt adhesive having moderate elasticity, strong cohesive force, and excellent adhesive strength is obtained. It is done.

  In the hot melt adhesive of the present invention, when a linear linear approximation line is drawn between tan δ at 90 ° C. and tan δ at 150 ° C. at 100 Hz of the loss tangent loss tan δ, the change in tan δ with respect to the temperature change is shown. Let tan δ slope. The value of the tan δ slope is preferably 0.10 or less, more preferably 0.08 or less, and particularly preferably 0.05 or less. By setting the tan δ slope to 0.10 or less, a hot melt adhesive having a small change in viscoelasticity with respect to a change in temperature and good coatability and adhesiveness can be obtained.

The loss tangent versus temperature at each temperature was measured using a dynamic viscoelasticity measuring device (type Rheogel-E4000).
(Measurement method of loss tangent versus temperature): The measuring apparatus was controlled by E4000-START software version 1.0.0. Using a slit shearing jig, a slit of 10 mm length × 10 mm width × 0.5 mm thickness was inserted into a sample of 13 mm long × 20 mm wide × 1 mm thick, and then heated to 170 ° C. to start a cooling program.
In the program test, the temperature was decreased at intervals of 3 ° C., a hold time of 15 seconds was taken every 5 ° C., and the frequency was maintained at 100 Hz. The initial strain at the beginning of the test is 5 μm, and the automatic strain option in the software is used to accurately maintain a load that can be accurately measured throughout the test. The options are set so that the maximum applied distortion allowed by the software is 1-10 g.
The automatic strain option provides strain control at each temperature according to the following procedure.
If the load is lower than 1 g, the strain is increased by 50% of the current value.
If the load is higher than 10 g, the strain is reduced by 50% of the current value.
When the load is 1 to 10 g, the measurement is performed without changing the strain at the temperature, and the loss tangent tan δ is calculated from the load and the strain by software.

As a method of applying the hot melt adhesive of the present invention to an adherend, for example, (1) a method of melting and coating the adherend, (2) a hot melt adhesive film or the like between the adherends. The method of melt-pressing after interposing is mentioned.
Examples of the method (1) include spiral coating, roll coating, slot coating, spray coating, control seam coating, omega coating, bead coating, etc., regardless of contact type or non-contact type. However, it is not limited to these methods. As a coating amount, 0.1-100 g / m < ² > is preferable in surface coating, More preferably, it is 1-850 g / m < ² >. (That is, preferably 0.1 g / m ² or more, more preferably 1 g / m ² or more, and preferably 100 g / m ² or less, more preferably 50 g / m ² or less). 0.005 to 1 g / m is preferable, more preferably 0.01 to 0.5 g / m (that is, 0.005 g / m or more is preferable, 0.01 g / m or more is more preferable, and 1 g / m or less is preferable). More preferably, it is 0.5 g / m or less.
The thickness of the film of the method (2) is not particularly limited, but is preferably 1 to 500 μm, more preferably 5 to 300 μm (that is, preferably 1 μm or more, more preferably 5 μm or more, and 500 μm or less, more Preferably 300 μm or less). In addition, there is no limitation in particular also about the film preparation method, What is necessary is just to be able to be set as the film form of predetermined thickness.
Moreover, 80-200 degreeC is preferable and, as for the melting temperature when applying to a to-be-adhered body, More preferably, it is 100-180 degreeC. The melt viscosity at the time of application is preferably 0.5 to 500 Pa · s, more preferably 1 to 100 Pa · s. That is, it is preferably 0.5 Pa · s or more, and more preferably 1 Pa · s or more. Moreover, it is preferably 500 Pa · s or less, and more preferably 100 Pa · s or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the following, “parts” indicates parts by weight.

Production Example 1
After putting 1000 parts of xylene into a stainless steel pressure reactor and replacing the inside of the container with nitrogen, the temperature was raised to 200 ° C. in a sealed state. At this temperature, 500 parts of styrene, 150 parts of dicyclopentadiene, 350 parts of 2-ethylhexyl acrylate, 1000 parts of paraffinic oil [Diana Process Oil PW-90; manufactured by Idemitsu Kosan Co., Ltd.] and di-t-butyl peroxide 2 .5 parts of the mixed solution 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 disappearance of the monomer by gas chromatography. Subsequently, xylene was distilled off from the polymer solution produced (150 ° C., 2 kPa) to obtain a copolymer (D-1). Tg of (D-1) was −20 ° C., Mn was 1,800, and SP value was 10.3.

Production Example 2
In Production Example 1, a copolymer (D) was prepared in the same manner as in Production Example 1, except that 700 parts of styrene and 300 parts of stearyl methacrylate were used instead of 500 parts of styrene, 150 parts of dicyclopentadiene and 350 parts of 2-ethylhexyl acrylate. -2) was obtained. Tg of (D-2) was −30 ° C., Mn was 1,600, and SP value was 10.1.

Production Example 4
700 parts of dibenzyl ether was put into a stainless steel pressure reactor, the inside of the container was purged with nitrogen, and the temperature was raised to 240 ° C. in a sealed state. At this temperature, 1000 parts of styrene was added dropwise over 4 hours, and further maintained at 240 ° C. for 3 hours to complete the polymerization. The end point of the reaction was confirmed by disappearance of the monomer by gas chromatography.
Subsequently, dibenzyl ether was distilled off (230 ° C., 1.3 kPa) from the resulting polymer solution to obtain a copolymer (E-1). Tg of (E-1) was 40 ° C., Mn was 1,800, and SP value was 10.5.

Examples 1-7 and Comparative Examples 1-45
The mixture of each component mixed with the formulation (parts by weight) shown in Table 1 was put into a stainless steel pressure reactor, and the inside of the container was purged with nitrogen. Then, the temperature was raised to 160 ° C. in a sealed state and stirred for 4 hours. The hot melt adhesive of the present invention and a comparative hot melt adhesive were obtained.

(Explanation of symbols, etc.)
A-1: Styrene-butadiene block copolymer rubber “Clayton D-1155” [manufactured by Kraton Polymer Japan Co., Ltd.] Styrene content 40% by weight; MI = 14 [corresponding to (a-1)]
A-2: Styrene-butadiene block copolymer rubber “Clayton D-1116” [manufactured by Kraton Polymer Japan Co., Ltd.] Styrene content: 23% by weight; MI = <1 [corresponding to (a-2)]
A-3: Hydrogenated styrene-isoprene block copolymer rubber “Septon 2002” [manufactured by Kuraray Co., Ltd.] 30% by weight of styrene; MI = 45 [corresponding to (a-1)]
B-1: Partially hydrogenated petroleum resin (C9 fraction copolymer main component) “Alcon M-115” [manufactured by Arakawa Chemical Co., Ltd.]; softening point = 115 ° C.
B-2: Hydrogenated petroleum resin (DCPD copolymer main component) “Escollet ECR-227E” (manufactured by Tonex); softening point = 125 ° C.
C-1: Naphthenic oil “Diana Process Oil NP-24” [Idemitsu Kosan Co., Ltd.]
C-2: Paraffinic oil “Diana Process Oil PW-90” [Idemitsu Kosan Co., Ltd.]
E-2: Polyphenylene oxide (poly-2,6-dimethyl-1,4-phenylene oxide) {Product name: Noryl PPOSA120, manufactured by GE Plastics, Mw 6350, SP value 11.2, Tg 160 ° C.}
F-1: Hindered phenol antioxidant “Irganox 1010” [manufactured by Ciba Specialty Chemicals]
F-2: Phosphorous antioxidant “ADK STAB 2112” [Asahi Denka Kogyo Co., Ltd.]
F-3: Benzotriazole UV absorber “Tinuvin 328” [manufactured by Ciba Specialty Chemicals Co., Ltd.]

Performance Test Example For each hot melt adhesive obtained in Examples 1 to 7 and Comparative Examples 1 to 45, the melt viscosity at 140 ° C., loss on heating, and 100 Hz with a BL type viscometer were measured according to the test method described above. The loss tangent loss tan δ at 90 ° C. and 150 ° C. was measured, and the tan δ slope from the linear linear approximation line was calculated. In addition, the following test methods were used to evaluate the T-type peel adhesion strength, the texture of the adhesive, the coatability, and the odor during melting. 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 T-type peel adhesion strength of the adhesive, the texture of the adhesive, the coatability, and the odor at the time of melting compared to the comparative example. It can be seen that the balance is remarkably excellent.

Test method (Adhesive texture)
A hot melt adhesive film having a thickness of 20 μm is sandwiched between a nonwoven fabric made of polypropylene having a thickness of 100 μm and bonded by heating and pressing at 150 ° C. Thereafter, the texture is evaluated by touch at room temperature.
Evaluation criteria ○: Does not impair the texture of the nonwoven fabric (same as no adhesive)
Δ: Inferior to the texture of the nonwoven fabric
×: The texture of the nonwoven fabric is remarkably impaired (coatability)
The hot melt adhesive is applied to the nonwoven fabric under the following conditions, and the coatability is confirmed by spiral coating.
Conditions Applicator used: MC-112 (manufactured by Nordson)
Gun head; spiral spray gun (manufactured by Nordson)
Nozzle; 18/1000 inch wide nozzle (manufactured by Nordson)
Coating temperature: 130 ° C
Line speed: 100 m / min Coating width: 20 mm
Application amount: 5 g / m ²
Evaluation criteria A: Coating pattern is not disturbed at all.
○: Coating pattern is somewhat disordered, but coating is possible.
X: Stable coating is not possible.
(T-type peel adhesion strength)
Each hot melt adhesive was applied to a polypropylene nonwoven fabric having a length of 100 mm × width 25 mm × thickness 100 μm in a bead shape with a width of 25 mm (coating temperature 150 ° C., coating amount 0.06 g / m). Laminated. After leaving for 24 hours in an atmosphere of 25 ° C., the peel strength is measured at a tensile speed of 300 mm / min using a tensile tester (Autograph AGS-500B (manufactured by Shimadzu Corporation)), and the maximum value is T-type. It was set as peel adhesive strength (unit: Ng / 25 mm).
(Odor when melted)
30 g of a sample of hot melt adhesive is put into a 200 ml glass bottle, covered with aluminum, and left in a 150 ° C. circulating air dryer for 60 minutes. Take out the bottle, immediately remove the aluminum lid, smell the odor, and evaluate the intensity of the odor by sensory evaluation.
The evaluation criteria are shown in Table 3.

The hot melt adhesive of the present invention is excellent in adhesive strength, cohesive strength, flexibility and processability, and has little odor. Therefore, a wide range of adherends (for example, various plastic molded articles, rubber, paper, cloth, metal, Applicable for bonding wood, glass, mortar concrete, etc. However, it is particularly suitable as a hot melt adhesive for bonding polyolefin (polyethylene, polypropylene, etc.) resin molded products, which are said to be hardly adhesive, or these and other adherends described above. Examples include adhesion between a polyolefin-based nonwoven fabric constituting a disposable diaper and a polyolefin-based film.
Examples of an adhesive body (the 23rd invention) in which polyolefin resin molded articles are bonded to each other or another adherend with the hot melt adhesive of the present invention include a disposable diaper, a disposable sanitary napkin, an adhesive tape, And adhesive films, automotive lamps, fabric products, clothing, labels, woodwork crops, various building materials, and the like.
The adhesive of the present invention can be used not only in a solid hot melt type, but also in the form of an organic solvent solution, an emulsion, a dispersion, a film and the like. The hot melt adhesive of the present invention can also be used as a moldability of various thermoplastic resins or thermosetting resins, a resin property modifier, an asphalt fluidity modifier, and the like.

Claims (10)

In a hot melt adhesive comprising a rubber (A) selected from a diene (co) polymer and an ethylene-α-olefin copolymer, a tackifier resin (B), and a plasticizer (C), the (A) is linear. A hot melt adhesive comprising two types of mold rubber (a-1) and radial mold rubber (a-2) as essential components. The hot melt adhesive according to claim 1, wherein the ratio of (a-1) to (a-2) is 10:90 to 90:10 by weight. The hot melt adhesive according to claim 1 or 2, wherein (A) is at least two selected from the group consisting of a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a hydrogenated product thereof. The hot melt adhesive according to any one of claims 1 to 3, further comprising a copolymer (D) having the following (i), (ii) and / or (iii) as a constituent monomer: Agent.
(i) Aromatic vinyl monomer (d-1)
(ii) C4-C20 aliphatic or alicyclic monounsaturated hydrocarbon (d-2)
(iii) alkyl or alkenyl (meth) acrylate (d-3) having 4 to 24 carbon atoms in the alkyl or alkenyl group 5. The hot resin according to claim 4, further comprising (co) polymer (E) having (d-1) as a constituent monomer and having a glass transition point higher than that of (D) by 10 ° C. or more. Melt adhesive. Based on the total weight of (A), (B), (C), (D) and (E), (A) is 5 to 40 wt%, (B) is 10 to 670 wt%, and (C) is The hot melt adhesive according to claim 5, comprising 1 to 30% by weight, 1 to 40% by weight of (D), and 0.1 to 30% by weight of (E). The hot melt adhesive according to any one of claims 1 to 6, wherein the loss on heating after 3 hours in an air atmosphere at 150 ° C is 0.01 to 2% by weight. The hot melt adhesive according to any one of claims 1 to 7, wherein the tangent loss tan δ at 90 ° C and 160 ° C under 100 Hz is 0.1 to 5.0 and 0.5 to 10.0, respectively. The hot melt adhesive according to claim 8, wherein the slope of loss tangent loss tan δ at 90 ° C and 150 ° C under 100 Hz is 200.1 or less. Adhesive body formed by bonding polyolefin resin molded products to each other or another adherend with the hot melt adhesive according to any one of claims 1 to 9.