JP2007077203A - Active energy ray curable hot melt adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactive hot melt adhesive which does not cause generation of a gas on curing reaction, reaches the final strength in a short time, and has good adhesiveness to a wide range of adherends. <P>SOLUTION: The active energy ray curable hot melt adhesive comprises a diene (co)polymer (A), a vinyl group-containing component (B), an active energy ray polymerization initiator (C), and a tackifying resin (D), and particularly the component (A) is at least one kind selected from the group consisting of a styrene-butadiene-styrene block copolymer rubber (SBS), a styrene-isoprene-styrene block copolymer rubber (SIS), and a partially hydrogenated product thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a reactive hot melt adhesive. More specifically, the present invention relates to an active energy ray-curable reactive hot melt adhesive.

The hot melt adhesive is a solid and solventless type, and can be used only with an operation of heating. In addition, since instant bonding and high-speed bonding are possible, it has economic advantages associated with improved productivity, so it focuses mainly on the fields of sanitary materials, packaging, bookbinding, building materials, automobiles, textile processing, electrical / electronics, etc. Is used. In particular, a moisture-curable reactive hot melt adhesive having an isocyanato group or a silyl group has recently attracted attention as being excellent in heat resistance and adhesiveness. (For example, patent document 1).
Japanese Patent Laid-Open No. 10-245536

However, moisture-curable reactive hot melt adhesives require several days to a week to complete the curing reaction and develop the final strength. Is difficult to apply and is accompanied by the generation of gas during the reaction, which may cause problems such as foaming depending on use conditions.
In addition, many of the adherends represented by polyethylene and polypropylene, which are generally called difficult adhesion, do not have sufficient adhesive strength.
An object of the present invention is to provide a reactive hot melt adhesive that reaches the final strength in a short time without generating gas during the curing reaction and has good adhesion to a wide range of adherends.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to an active energy ray-curable hot melt adhesive comprising a diene (co) polymer (A), a vinyl group-containing component (B), an active energy ray polymerization initiator (C) and a tackifying resin (D). A cured product obtained by curing the adhesive; an adhesive bonded by the adhesive.

The reactive hot melt adhesive of the present invention has a rapid development of final strength and excellent adhesion strength to difficult-to-adhere adherends as compared with conventional moisture-curing reactive hot melt adhesives. Since no gas is generated during the reaction, problems such as foaming do not occur.

  As the diene (co) polymer (A) which is the first component constituting the hot melt adhesive of the present invention, a monomer (for example, butadiene, isoprene, etc.) composed of 4 to 18 carbon atoms or this and A (co) polymer having other monomers (weight ratio of diene to other monomers: 0.1 to 100: 0 to 99.9) and a partially hydrogenated product thereof are included. Other monomers include aromatic vinyl monomers having 8 to 20 carbon atoms (such as styrene), olefins having 2 to 8 carbon atoms (such as ethylene and propylene), and unsaturated nitriles having 3 to 20 carbon atoms. (For example, acrylonitrile etc.) etc. are mentioned.

The number average molecular weight (hereinafter referred to as Mw) of (A) is preferably 1,000 to 1,000,000, and more preferably 2,000 to 700,000. Mw is a value determined by gel permeation chromatography (GPC) using polystyrene as a standard. The same applies to the number average molecular weight (hereinafter referred to as Mn) described below.
The iodine value of (A) is preferably 0.1 to 1000, more preferably 0.5 to 500 from the viewpoint of adhesive strength. The iodine value is a value measured according to JIS K-1525.

Specific examples of the diene (co) polymer (A) include butadiene rubber, isoprene rubber, natural rubber, butyl rubber, nitrile rubber, acrylonitrile-butadiene copolymer rubber (NBR), and styrene-butadiene-styrene block copolymer rubber. (SBS), styrene-isoprene-styrene block copolymer rubber (SIS), styrene-isoprene-butadiene-styrene block copolymer rubber (SIBS), styrene-butadiene random copolymer rubber (SBR), diene (co) polymer rubber Hydrogenated partially hydrogenated diene part [SIS (partially) hydrogenated (SEPS), partially hydrogenated SBS, partially hydrogenated SBR, styrene-butadiene-isoprene-styrene block copolymer rubber Partially hydrogenated product (SEEPS)
) Etc.].
As specific examples of SBS, specific examples of SIS such as “Clayton D-1155” (styrene content 40% by weight) manufactured by Clayton Polymer Co., Ltd., “Toughprene 315” (styrene content 20% by weight) manufactured by Asahi Kasei Chemicals Corporation, etc. As a specific example of SIBS, such as “Clayton D-1107” (styrene content 15% by weight) manufactured by Kraton Polymer Co., Ltd., “SIBSTER 102T” manufactured by Kaneka Co., Ltd. Specific examples of “SBR 1507” manufactured by Rubber Co., Ltd., “Septon 2063” manufactured by Kuraray Co., Ltd. (styrene content: 13% by weight) and the like, and specific examples of SEBS include “Clayton manufactured by Kraton Polymer Co., Ltd.” Specific examples of SEEPS such as “G1651” (styrene content 33% by weight) include “Septon” manufactured by Kuraray Co., Ltd. 033 "(styrene content 30 wt%), and the like, respectively.

Of these, (A) is preferably SBS, SIS or a partially hydrogenated product thereof from the viewpoint of adhesive strength.
(A) may be used alone or in combination of two or more.

  Specific examples of the vinyl group-containing component (B) that is the second component constituting the hot melt adhesive of the present invention include the following, and these may be used alone or in combination of two or more. .

(B1) Mono (meth) acrylate (B11) Alkyl (C4-50) (meth) acrylate Lauryl (meth) acrylate and stearyl (meth) acrylate etc. (B12) Aliphatic monool (C1-30) alkylene oxide (AO) (C2-4) 1-30 mol adduct (meth) acrylate (meth) acrylate of lauryl alcohol (hereinafter referred to as EO) 2 mol adduct (meth) acrylate and propylene oxide of lauryl alcohol (hereinafter referred to as PO) (Notation) (Meth) acrylate of 3 mol adduct (B13) AO (C2-4) 1-30 mol adduct of phenol or alkylphenol (C7-30) (meth) acrylate ) 1 mol EO of acrylate and nonylphenol Of Addendum the (meth) acrylate (B14) cycloaliphatic monools (C6-30) (meth) acrylate cyclohexyl (meth) acrylate and isobornyl (meth) acrylate

(B2) di (meth) acrylate (B21) (poly) oxyalkylene (C2-4) (molecular weight 62-Mn3,000) di (meth) acrylate polyoxyethylene (Mn400) di (meth) acrylate, polyoxy Di (meth) acrylate of di (meth) acrylate of propylene (Mn200) and di (meth) acrylate of polyoxytetramethylene (Mn650) etc. (B22) AO (C2-4) 2-30 mol adduct of bisphenol A di (meth) acrylate bisphenol Di (meth) acrylate of EO2 mol adduct of A and di (meth) acrylate of PO4 mol adduct of bisphenol A, etc. (B23) Di (meth) acrylate of aliphatic polyol (C2-30) Trimethylolpropane di (meta ) Acrylate, neopentyl glycol di (meth) Chryrate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc. (B24) di (meth) acrylate of alicyclic polyol (C6-30) dimethylol tricyclodecanedi (meth) Acrylate, cyclohexanedimethanol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A, etc.

(B3) poly (trivalent to hexavalent or higher) (meth) acrylate (B31) polyvalent (trivalent to hexavalent or higher) alcohol (C3-40) poly (meth) acrylate trimethylolpropane tri ( (Meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane PO3 molar adduct tri (meth) acrylate, trimethylolpropane EO 3 molar adduct tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, etc.

(B4) Polyester (meth) acrylate A plurality of ester bonds obtained by esterification with a polyvalent (divalent to tetravalent) carboxylic acid, a polyvalent (divalent to hexavalent) alcohol, and a (meth) acryloyl group-containing compound Polyester (meth) acrylate having a plurality of (meth) acryloyl groups and a molecular weight of 150 to Mn 4,000 As the polyvalent (divalent to tetravalent) carboxylic acid, for example, an aliphatic polyvalent carboxylic acid [C3 to 20, for example, maleic acid (Anhydrides), adipic acid, sebacic acid, succinic acid, maleic acid and dipentaerythritol dicarboxylic acid (reactant of dipentaerythritol and acid anhydride)], alicyclic polycarboxylic acid [C5-30, eg cyclohexane Dicarboxylic acid, tetrahydro (anhydride) phthalic acid and methyltetrahydro (anhydride) phthalic acid] and aromatic poly Carboxylic acid [C8-30, for example isophthalic acid, terephthalic acid, phthalic acid (anhydride) and trimellitic acid (anhydride)] and the like.
Examples of the polyhydric (divalent to hexavalent) alcohol include C2-30, for example, dihydric alcohol [for example, C2-12 aliphatic dihydric alcohol [(di) alkylene glycol, such as ethylene glycol, diethylene glycol, propylene glycol, 1, 6-hexanediol, neopentylglycol and dodecanediol]; C6-10 alicyclic dihydric alcohols [eg 1,4-cyclohexanediol and cyclohexanedimethanol]; and C8-20 aromatic dihydric alcohols [eg xyly. Lenglycol and bis (hydroxyethyl) benzene]] and trihydric to octahydric or higher polyhydric alcohols [eg (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [eg glycerin, trimethylolpropane, penta] Erisrit , Sorbitan, sorbitol, dipentaerythritol, diglycerin and other polyglycerols] and saccharides and derivatives thereof [for example, sucrose, glucose, fructose, mannose, lactose, and glycosides (such as methyl glucoside)].
Examples of the (meth) acryloyl group-containing compound include C2-30, such as (meth) acrylic acid and hydroxymethyl (meth) acrylate.

(B5) Siloxane polymer having an ethylenically unsaturated group in the main chain and / or side chain of dimethylpolysiloxane [Mn 300 to 20,000, for example, dimethylpolysiloxane di (meth) acrylate]

(B6) Mw = 68-5,000 aliphatic alkadienes (for example, pentadiene, hexadiene, divinyl adipate, etc.), Mw = 130-10,000 aromatic alkadienes (for example, divinylbenzene, etc.)

Of these (B), (B23) and (B31) are preferred, and trimethylolpropane di- or tri- (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Pentaerythritol tri-, tetra- (meth) acrylate, dipentaerythritol, tri-, tetra-, penta-, hexa- (meth) acrylate and mixtures thereof, or polymers thereof.
The preferable Mn of (B) is 100 to 30,000. When the molecular weight is 100 or more, the residual monomer after curing that causes odor is less likely to volatilize, and when it is 30,000 or less, the coatability of the hot melt adhesive is better.
Of these (B), the boiling point at normal pressure is preferably higher than 100 ° C, more preferably higher than 120 ° C. If the boiling point at normal pressure exceeds 100 ° C, the possibility of boiling or volatilization during hot melt coating is small.
In the hot melt adhesive of the present invention, the ratio [(B) / (A)] of the number of double bonds (B) and the number of double bonds (A) is preferably 500/1 to 0.5 / 1, more preferably 300/1 to 1/1.

  The active energy ray polymerization initiator (C), which is the third component constituting the hot melt adhesive of the present invention, is added to cure the hot melt adhesive of the present invention by active energy ray irradiation. (C) is a hydroxybenzoyl compound {2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, 2,2-dimethoxy-1,2-diphenylethane -1-one etc.}, benzoylformate compound (methylbenzoylformate etc.), thioxanthone compound (isopropylthioxanthone etc.), benzophenone compound (benzophenone etc.), phosphate ester compound (1,3,5-trimethylbenzoyldiphenylphosphine oxide) Etc.) and benzyl dimethyl ketal.

As the tackifying resin (D) which is the fourth component constituting the hot melt adhesive of the present invention, a known resin {for example, described in Adhesion Technology 20, (2), 13 (2000)} or the like is used. For example, rosin, rosin derivative resin [eg, polymerized rosin, rosin ester, etc .: number average molecular weight (hereinafter referred to as Mn) 200 to 1,000], terpene resin [eg, α-pinene, β-pinene, limonene, etc. (Co) polymers and their phenol modifications: Mn 300 to 1200], coumarone-indene resin (Mn 300 to 1200), petroleum resin [for example, C5 fraction, C9 fraction, C5 / C9 fraction, dicyclopentadiene (Co) polymers such as 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, from the viewpoints of thermal stability, odor and hue, hydrogenated terpene resins and hydrogenated petroleum resins are preferred, and more preferred are C9 fraction and C5 / C9 fraction ( A hydrogenated product of a (co) polymerized petroleum resin and a hydrogenated product of a (co) polymerized petroleum resin of dicyclopentadiene.

  The content (% by weight) of the diene (co) polymer (A) is preferably 5 or more from the viewpoint of adhesive strength based on the total weight of (A), (B), (C) and (D). More preferably, it is 10 or more. From the viewpoint of coatability, it is preferably 50 or less, more preferably 40 or less.

The vinyl group-containing component (B) content (% by weight) is 5 or more based on the total weight of (A), (B), (C) and (D) from the viewpoint of resin strength after curing. More preferably, it is 10 or more. Moreover, from a viewpoint used as a hot melt, 50 or less is preferable, More preferably, it is 40 or less.

  The content (% by weight) of the active energy ray polymerization initiator (C) is 0.001 or more based on the total weight of (A), (B), (C) and (D) from the viewpoint of the curing rate. Is more preferable, and 0.002 or more is more preferable. Moreover, from a viewpoint of the reach | attainment depth of an active energy ray, 10 or less is preferable, More preferably, it is 8 or less.

  The content (% by weight) of the tackifier (D) is preferably 15 or more from the viewpoint of improving the adhesive strength based on the total weight of (A), (B), (C) and (D). Preferably it is 20 or more. Moreover, from a viewpoint of improving a softness | flexibility, 85 or less are preferable, More preferably, it is 80 or less.

You may add a plasticizer (E) to the hot melt adhesive of this invention as needed. As (E), known plasticizers [adhesion techniques 20, (2), 21 (2000), etc.] can be used, such as paraffinic, naphthenic or aromatic process oil, liquid polybutene, liquid polybutadiene, and the like. Liquid resins such as liquid polyisoprene (Mw = 300 to 10,000), hydrogenated products of these liquid resins, natural or synthetic waxes {paraffin wax, microcrystalline wax and low molecular weight polyolefin wax (Mw = 1,000 to 30,000) etc., and a mixture of two or more thereof.
Of these, paraffinic process oil, naphthenic process oil, and mixtures thereof are preferred from the viewpoints of thermal stability and weather resistance.

  The amount of the plasticizer (E) used is usually 40% or less, preferably 35% or less, based on the total weight of the hot melt adhesive [(A) + (B) + (C) + (D)] of the present invention. It is.

The hot melt adhesive of the present invention can contain other additives (F) as necessary.
Other additives (F) include antioxidants {hindered phenol compounds [pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3. -(3,5-di-t-butyl-4-hydroxyphenyl) propionate etc.], phosphorus compounds [tris (2,4-di-t-butylphenyl) phosphite etc.], sulfur compounds [pentaerythryl -Tetrakis (3-lauryl thiopropionate) and dilauryl-3,3'-thiodipropionate etc.], etc.}, ultraviolet absorber {benzotriazole-based compound [2- (3,5-di-t-amyl- 2-hydroxyphenyl) benzotriazole and 2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.]}, light stabilizer {H Nard amine compound [(bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.]}, adsorbent (alumina, silica gel and molecular sieve etc.), silane coupling agent, organic or inorganic filling Agents (talc, mica, calcium carbonate, titanium oxide, calcium oxide, etc.), dispersants {for example, organic dispersants [formalin condensate of naphthalenesulfonate, polystyrenesulfonate, polyacrylate, polycarboxylate, Carboxymethyl cellulose and polyvinyl alcohol, polyoxyalkylene, polyhydric alcohol, carboxylate, carboxylate, sulfate, sulfonate, phosphate, primary to tertiary amine salt, quaternary ammonium salt, etc.] and inorganic dispersant (Alkali metal salt of polyphosphoric acid and phosphoric acid dispersant, etc.), Bacteriostat, fungicide, pigments, dyes, and perfumes can be used.

The amount of (F) used is based on the total weight of the hot melt adhesive [(A) + (B) + (C) + (D)] of the present invention, an antioxidant, an ultraviolet absorber, and a light stabilizer. In antibacterial agents, antifungal agents, and perfumes, it is preferably 5% or less, and more preferably 3% or less. In the case of a silane coupling agent, a filler, a dispersant, a pigment, and a dye, it is preferably 50% or less, and more preferably 30% or less.

  The melt viscosity at 110 ° C. of the hot melt adhesive of the present invention is preferably 300 to 200,000 mPa · s, more preferably 500 to 100,000 mPa · s from the viewpoint of coating properties. The softening point is preferably 20 to 100 ° C, more preferably 30 to 90 ° C.

The production of the hot melt adhesive of the present invention is carried out by previously blending components other than (B) and (C), and finally blending (B) and (C) (Method-1), or hot melt adhesive. The method (Method-2) which mix | blends each component of 1 simultaneously is mentioned.
Preferred is (Method-1).

In producing a hot melt adhesive, the components of the adhesive are heated, melted,
Any material that can be kneaded can be used, and ordinary hot-melt production equipment can be used.
Examples thereof include a mixer having a highly compressible screw or ribbon stirrer, a single or twin screw extruder, a sigma blade mixer, a ribbon blender, a butterfly mixer, and a kneader. The mixing temperature is preferably 60 to 250 ° C.

The hot melt adhesive of the present invention is appropriately formed into a desired shape such as a block, pellet, powder, sheet or film. A pelletizer, a pulverizer, an extruder or the like is used for molding.
The method for using the hot melt adhesive of the present invention is not particularly limited. For example, when the adhesive is in the form of a block or a pellet, the adhesive is melted and then bonded to a substrate to be bonded. Used by applying.

As an apparatus used for application, an applicator for a normal hot melt adhesive, [for example, a roll coater having a heatable melting tank (gravure roll, reverse roll, etc.), curtain coater, bead, spiral, spray, slot] and Extruders [for example, single screw extruders, twin screw extruders, kneader ruders, etc.].
In the case of the former applicator, an adhesive can be applied to one or both of the adherends and bonded together before cooling and solidification, or after cooling and solidification, the adherends can be combined, heated and bonded again. When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification.
In the case of the latter extruder, extrusion is performed on one or both of the adherends, and after cooling and solidification, the adherends are combined, heated again, and bonded. When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification. Moreover, it can coextrude between adherends and can perform bonding simultaneously.
The melting temperature when applied to the adherend is usually 60 to 200 ° C, preferably 80 to 180 ° C.

The curing reaction of the reactive hot melt adhesive of the present invention starts when the active energy ray polymerization initiator is decomposed and starts polymerization by irradiation with active energy rays. The curing temperature is usually 5 to 50 ° C. The curing time is usually 5 minutes or less.
The cured product thus obtained has good cured properties and excellent heat resistance.

  The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, infrared rays and visible rays. Of these active energy rays, ultraviolet rays and electron beams are preferable from the viewpoint of curability and resin deterioration, and ultraviolet rays are more preferable.

When the hot melt adhesive of the present invention is cured by ultraviolet irradiation, various ultraviolet irradiation apparatuses (Eye Grandage [trade name, manufactured by Eyegraphic Co., Ltd.], metal halide lamp, etc.) can be used. The dose of the ultraviolet radiation is typically 10~10,000mJ / cm ^2, preferably lower from the viewpoint of the curability of the hot melt adhesive is preferable upper limit in view of flexibility of 100 mJ / cm ^2, the cured product 5,000J / Cm ² .

  When the hot melt adhesive of the present invention is cured by electron beam irradiation, various electron beam irradiation apparatuses [for example, Electron Beam, manufactured by Iwasaki Electric Co., Ltd.] can be used. The irradiation amount of the electron beam is usually 0.5 to 20 Mrad, and the preferable lower limit is 1 Mrad from the viewpoint of curability of the hot melt adhesive, from the viewpoint of avoiding damage to the cured product or the base material, and flexibility of the cured product. The preferred upper limit is 15 Mrad.

  The hot melt adhesive of the present invention is usually cured by an active energy ray, but can be cured by heat when a thermosetting catalyst is contained if necessary. (The curing start temperature of the thermal effect catalyst is desirably 40 ° C. or more higher than the softening point of the hot melt adhesive.)

When the adhesive is powder, it is used after being applied to the adherend and then heated and bonded. The heating temperature is not particularly limited, but is preferably 10 to 20 ° C. higher than the melting point (or softening point). When bonding, it is better to pressurize, and the pressure can be released after cooling and solidification. The pressure to be applied is not particularly limited as long as sufficient adhesion can be obtained, and is preferably 10 kPa to 5 MPa. The basis weight of the powder is not particularly limited as long as a desired adhesive force can be obtained, but is preferably 10 to 500 g / m ² .
When the adhesive is a sheet or a film, the adhesive is sandwiched between substrates to be bonded together, heated and melted and bonded, or placed on one or both, heated and melted, and before cooling and solidification Or after cooling and solidification, the adherends are combined, heated again and bonded together. The heating temperature at the time of heating and melting is not particularly limited, but it is better that the heating temperature is 10 to 20 ° C. higher than the melting point (or softening point). Moreover, it is better to pressurize when bonding, and the pressure can be released after cooling and solidification. The pressure to be applied is not particularly limited as long as a desired adhesive force can be obtained, and is preferably 10 kPa to 5 MPa.
The size of the sheet or film is not particularly limited as long as it has a desired area. Although the thickness of a sheet | seat or a film does not have a restriction | limiting in particular, Preferably it is 10-500 micrometers, More preferably, it is 30-300 micrometers.

The hot melt adhesive of the present invention can be used as an adhesive for the following applications, and particularly, since it has good durability and adhesiveness, it is also suitable for bonding materials that require heat resistance after bonding. Can be used.
For building materials: Wood adhesive (plywood, particle board, hardboard, laminated wood and woodworking adhesive) and other building material adhesive (concrete, mortar, wallpaper, flooring and Tile adhesive),
For fiber materials: Adhesives for fiber materials (nonwoven fabrics, flocking, adhesive fabrics, adhesive sewing and adhesives for carpet backing),
For other materials: Plastic adhesives (for hard vinyl chloride pipes, soft vinyl chloride and foam plastic adhesives), rubber adhesives, leather adhesives, ceramics adhesives (for multi-layer glass, optical lenses and Abrasive materials), bioadhesives (dental, surgical and adhesive adhesives), (household adhesives (for paper, etc.), cardboard adhesives, bookbinding adhesives, electrical appliance adhesives, etc. .

The bonded body of the present invention is a material obtained by bonding a material to be bonded using the above active energy ray-curable hot melt adhesive, and may be formed by a molding machine at the same time as or after bonding. Good. As an adherend material, the material used in each of the above applications can be used.

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

Examples 1 to 5 and Comparative Example 1
Among the components of the formulation shown in Table 1, components other than the vinyl group-containing component and the polymerization initiator (B-1, B-2, C-1, C-2) are charged into a stainless steel pressure reactor. The mixture was heated to 160 ° C. and melted and mixed with stirring for 4 hours. After cooling to 120 ° C., the vinyl group-containing component and the polymerization initiator were added, and melted and mixed with stirring for 3 hours. Hot melt adhesives and comparative hot melt adhesives were obtained.

(Explanation of symbols, etc.)
A-1: Styrene-butadiene-styrene block copolymer rubber {trade name: Kraton D-1155, manufactured by Kraton Polymer Co., Ltd., styrene content 40% by weight, MI = 14, Mw = 90,000, iodine value = 282}
A-2: Styrene-isoprene-styrene block copolymer rubber {Product name: SIS-5002, manufactured by Nippon Synthetic Rubber Co., Ltd., styrene content 22% by weight, MI = 1.5, Mn = 180,000, iodine value = 287}
B-1: Dipentaerythritol hexaacrylate {Brand name: Neomer DA-600, manufactured by Sanyo Chemical Industries, Mn = 540}
B-2: 1,6-hexanediol diacrylate {Brand name: Light acrylate 1.6HX-A, manufactured by Kyoeisha Chemical Co., Ltd., Mn = 230}
C-1: 1-hydroxycyclohexyl phenyl ketone {Brand name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.}
C-2: 2,2-dimethoxy-1,2-diphenylethane-1-one {trade name: IRGACURE 651, manufactured by Ciba Specialty Chemicals Co., Ltd.}
D-1: Hydrogenated copolymer of dicyclopentadiene and petroleum resin {Product name: Escorez E-5600, manufactured by Tonex Co., Ltd., softening point = 100 ° C.}
E-1: Paraffinic process oil {Product name: Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.}

Comparative Example 2
In a separable flask equipped with a temperature control device and a stirrer, 15.0 parts of “Placcel 305” (manufactured by Daicel Chemical Industries; Made by Kogyo Co., Ltd .: Polyester diol composed of 1,6-hexanediol and adipic acid, hydroxyl value = 23.3, Mn = 4,800) 85.0 parts were charged, dissolved at 120 ° C., and then dehydrated under reduced pressure (120 ° C., 133 Pa, 1 hour). In a nitrogen atmosphere, 29.2 parts of MDI was added and aged at 80 ° C. for 4 hours to obtain a moisture-curable reactive hot melt adhesive.

About said hot-melt-adhesive, 110 degreeC melt viscosity and resin strength, hardening time, and adhesive strength were evaluated with the following test methods.
The results are shown in Table 2.

<110 ° C. melt viscosity measurement method>
Based on JIS K7117-1987 (SB type viscometer, SB4 spindle), the melt viscosity at 110 ° C. was measured.
<Adhesive strength evaluation method>
Each hot melt adhesive was applied in a bead shape with a width of 25 mm to a PET film having a thickness of 100 mm × 25 mm × 50 μm in the hot melt adhesive of Example or Comparative Example (application temperature 180 ° C., application amount 0.06 g / m), A test piece was obtained by laminating PP films of the same size.
About Examples 1-3 or Comparative Example 1, this was cured by irradiating ultraviolet rays at 2,000 mJ / cm ² with an ultraviolet irradiation device (Eye Grandage) to obtain test pieces. The peel strength of this test piece was measured at a tensile speed of 300 mm / min using a tensile tester [Autograph AGS-500B (manufactured by Shimadzu Corporation)], and the maximum value was defined as the adhesive strength (unit: N / 25 mm).
For Comparative Example 2, this was left for 1 week in a constant temperature and humidity chamber at 23 ° C. and 50% RH to be cured. The test piece was measured for peel strength at a tensile speed of 300 mm / min using a tensile tester (Autograph AGS-500B; manufactured by Shimadzu Corporation), and the maximum value was defined as adhesive strength (unit: N / 25 mm). ).

<Method for measuring resin strength after curing>
The hot melt adhesives of Examples or Comparative Examples were molded to a thickness of 1 mm with a hot press (using SA-302 manufactured by Tester Sangyo Co., Ltd.), and No. 3 dumbbells were punched out to obtain test pieces.
About Examples 1-3 or the comparative example 1, this was hardened by irradiating ultraviolet rays at 2,000 mJ / cm ² with an ultraviolet irradiation device (Eye Grandage). Using this test piece, the tensile breaking strength of the resin was measured at a tensile speed of 300 mm / min using a tensile tester (Autograph AGS-500B; manufactured by Shimadzu Corporation), and this breaking strength was defined as the resin strength ( Unit: MPa).
For Comparative Example 2, this was left for 1 week in a constant temperature and humidity chamber at 23 ° C. and 50% RH to be cured. Using this test piece, the tensile breaking strength of the resin was measured at a tensile speed of 300 mm / min using a tensile tester (Autograph AGS-500B; manufactured by Shimadzu Corporation), and this breaking strength was defined as the resin strength ( Unit: MPa).

<Curing time>
For Examples 1 to 3 and Comparative Example 1, the working time required for the ultraviolet irradiation (2,000 mJ / cm ² ) was defined as the curing time. Compared to those irradiated with 2,000 mJ / cm ^{2 of} ultraviolet light and those irradiated with 4,000 mJ / cm ² , there was no difference in resin strength, so that it was sufficiently cured by irradiation of 2,000 mJ / cm ² . The time required for the irradiation of 2,000 mJ / cm ² was taken as the curing time.
For Comparative Example 2, the resin strength was measured every 48 hours, and the time when the change in the resin strength was less than 5% was taken as the curing time.

Claims (5)

An active energy ray-curable hot melt adhesive comprising a diene (co) polymer (A), a vinyl group-containing component (B), an active energy ray polymerization initiator (C) and a tackifying resin (D). (A) is styrene-butadiene-styrene block copolymer rubber (SBS)
The hot melt adhesive according to claim 1, which is at least one selected from the group consisting of styrene-isoprene-styrene block copolymer rubber (SIS) and partially hydrogenated products thereof. The hot melt adhesive according to claim 1 or 2, wherein the melt viscosity at 110 ° C is 300 to 200,000 mPa · s. Hardened | cured material formed by hardening the adhesive agent in any one of Claims 1-3 by irradiation of an active energy ray. The adhesive body formed by adhere | attaching a to-be-adhered body with the adhesive agent in any one of Claims 1-4.