JP2007146145A - Hydrophilic hot-melt adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hot-melt adhesive having excellent adhesion even when an adherend is wet, so as to solve the problem wherein a conventional hot-melt adhesive, when it becomes wet, greatly decreases its adhesion. <P>SOLUTION: The hot-melt adhesive comprises: (A) a block polymer having a structure in which a block of (a) a polyolefin, and a block of (b) a hydrophilic polymer having a volume resistivity value of 1×10<SP>5</SP>to 1×10<SP>11</SP>Ωcm are alternately and repeatedly bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, and an imide bond; (B) a diene copolymer; and (C) a tackifier resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an adhesive. More specifically, the present invention relates to a hot melt adhesive having excellent hydrophilicity.

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.
Conventionally, as hot-melt adhesives used for bonding polyolefin films, nonwoven fabrics, paper, resin molded products, etc., liquid plasticizers such as tackifying resin components and process oils, other additives, etc. are added to diene copolymers. The thing etc. which mix | blend (for example, refer patent document 1) are known.

JP-A-8-60121

However, since the conventional hot melt adhesive is hydrophobic, there is a problem that the adhesive strength is extremely lowered when the adherend is wet with water. For example, in relation to sanitary materials, hot melt adhesives are also used for bonding hydrophilic nonwoven fabrics or tissues such as paper diapers and polyethylene or polypropylene. However, when these adherends are wet with water, interfacial peeling is likely to occur between the hot melt adhesive and the hydrophilic non-woven fabric or tissue, and the bonded portion may be peeled off.
An object of the present invention is to provide a hot melt adhesive that exhibits good adhesion even when the adherend is wet with water.

As a result of intensive studies to solve the above problems, the present inventors have found that a hot-melt adhesive containing a specific polymer having hydrophilicity can solve the above problems, and have reached the present invention.
That is, the present invention comprises a block of polyolefin (a) and a volume resistivity of 1 × 10 ⁵ to
A structure in which a block of 1 × 10 ¹¹ Ω · cm hydrophilic polymer (b) is repeatedly bonded alternately through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond A hydrophilic hot-melt adhesive comprising a block polymer (A) having a diene copolymer (B) and a tackifying resin (C); an adhesive bonded with the adhesive.

The hot melt adhesive of the present invention is extremely useful because it has the following effects.
(1) Good adhesion is exhibited even when the adherend is wet with water.
(2) Since the component imparting hydrophilicity is a polymer, there is no decrease in hydrophilic performance due to bleeding out or the like.

The block polymer (A) has a block of polyolefin (a) and a volume resistivity of 1
A block of hydrophilic polymer (b) of × 10 ⁵ to 1 × 10 ¹¹ Ω · cm is an ester bond,
It has a structure in which they are alternately and repeatedly bonded through at least one bond selected from the group consisting of an amide bond, an ether bond and an imide bond.
As the block of (a), a polyolefin (a1) having a carbonyl group (preferably a carboxyl group, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (a2) having a hydroxyl group at both ends of the polymer, and an amino group of the polymer Polyolefin (a3) having both ends can be used. Further, polyolefin (a4) having a carbonyl group at one end of the polymer, polyolefin (a5) having a hydroxyl group at one end of the polymer, and amino group at one end of the polymer Polyolefin (a6) can be used. Of these, polyolefins (a1) and (a4) having a carbonyl group are preferable because of easy modification.

As (a1), both polyolefins (a0) having a polyolefin which can be modified at both ends as a main component (content 50% by weight or more, more preferably 75% by weight or more, particularly preferably 80 to 100% by weight) are used. Examples thereof include those having a carbonyl group introduced at the terminal.
(A0) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a terminal group that can be modified. Those are preferred.

  (A0) is obtained by (co) polymerization (meaning polymerization or copolymerization; the same applies hereinafter) of one or a mixture of two or more olefins having 2 to 30 carbon atoms (hereinafter abbreviated as C). Polyolefin [polymerization method] and low molecular weight polyolefin [thermal degradation method] obtained by thermal degradation method of high molecular weight polyolefin (polyolefin obtained by polymerization of C2-30 olefin) can be used.

Examples of the C2-30 olefin include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin, and C4-30 (preferably 4-18, more preferably 4-4). And dienes of 8).
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, 1,4- Examples include pentadiene, 1,6-hexadiene, cyclopentadiene, and 1,11-dodecadiene.
Among these, C2-12 (ethylene, propylene, C4-12 α-olefin, butadiene and / or isoprene, etc.) is more preferable from the viewpoint of compatibility with the diene copolymer (B) described later. Are C2-10 (ethylene, propylene, C4-10 alpha-olefins and / or butadiene, etc.), particularly preferably ethylene, propylene and / or butadiene.

The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained by, for example, the method described in JP-A-3-62804.
The polyolefin obtained by the polymerization method can be produced by a known method, for example, easily by a (co) polymerization of the olefin in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst, a Ziegler-Natta catalyst, or the like. Obtainable.
As the radical catalyst, known ones such as di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-dicarbonate ester, azo compound, etc., and oxidized to γ-alumina carrier For example, molybdenum is attached.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support.
Examples of Ziegler catalysts and Ziegler-Natta catalysts include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .
Of the polyolefins obtained by the polymerization method or the thermal degradation method, low molecular weight polyolefins by the thermal degradation method are preferred from the viewpoint of ease of introduction of a carbonyl group, which is a modifying group, and availability.

The number average molecular weight (hereinafter abbreviated as Mn) by gel permeation chromatography (GPC) of (a0) is preferably 800 to 20,000, more preferably 1,000 to 10,000, from the viewpoint of coatability. Particularly preferred is 1,200 to 6,000.
The amount of double bonds in (a0) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per 1,000 C from the viewpoint of compatibility.
The average number of double bonds per molecule is preferably 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.5 to from the viewpoints of repetitive structure formation and compatibility. 2.5, most preferably 1.8 to 2.2.
In the thermal degradation method, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 in the range of 800 to 6,000 Mn can be easily obtained [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

The measurement conditions of Mn are as follows (hereinafter, Mn is measured under the same conditions).
Apparatus: High-temperature gel permeation chromatography Solvent: Orthodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel MIXED-B
Column temperature: 135 ° C

  As the polyolefin (a1) having carbonyl groups at both ends of the polymer, both ends of (a0) are α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its C1-4 Means an alkyl ester or an anhydride thereof. The same shall apply hereinafter.) Polyolefin (a11) having a structure modified with (a11), polyolefin (a12) having a structure obtained by secondary modification of (a11) with a lactam or an aminocarboxylic acid, (a0 And polyolefin (a13) having a structure obtained by oxidation or hydroformylation modification), polyolefin (a14) having a structure obtained by secondary modification of (a13) with lactam or aminocarboxylic acid, and a mixture of two or more of these.

(A11) can be obtained by modifying (a0) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride), C3-12 carboxylic acid, for example, monocarboxylic acid [(meth) acrylic acid etc.], dicarboxylic acid (maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.) ), These alkyl (C1-4) esters [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.], and anhydrides thereof.
Of these, from the viewpoint of reactivity with (a0), dicarboxylic acids, their alkyl esters and their anhydrides are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid is particularly preferred. (Anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used is preferably from 0.5 to 40% by weight, more preferably from the viewpoint of the repeatability and compatibility based on the weight of the polyolefin (a0). Is 1 to 30% by weight, particularly preferably 2 to 20% by weight.
Modification of the polyolefin (a0) with an α, β-unsaturated carboxylic acid (anhydride) is carried out by a known method, for example, the terminal double bond of (a0) is subjected to α, It can be carried out by thermally adding (ene reaction) β-unsaturated carboxylic acid (anhydride).
In the solution method, α, β is added to (a0) in the presence of a hydrocarbon solvent such as xylene or toluene.
-The method of adding unsaturated carboxylic acid (anhydride) and making it react at 170-230 degreeC in inert gas atmosphere, such as nitrogen, etc. are mentioned.
Examples of the melting method include a method in which (a0) is heated and melted, and then α, β-unsaturated carboxylic acid (anhydride) is added and reacted at 170 to 230 ° C. in an inert gas atmosphere such as nitrogen. Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(A12) can be obtained by secondary modification of (a11) with lactam or aminocarboxylic acid.
Lactams include C6-12 (preferably 6-8, more preferably 6) lactams such as caprolactam, enantolactam, laurolactam and undecanolactam.
As aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid, for example, amino acid (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid , Ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferable from the viewpoint of the reactivity of secondary modification, and caprolactam is more preferable. Laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid.
The amount of the lactam or aminocarboxylic acid used is preferably from the viewpoint of compatibility, preferably 0.1 to 20 lactams or aminocarboxylic acids per residue obtained by removing the carboxyl group from the α, β-unsaturated carboxylic acid, More preferably, it is 0.3-15, Most preferably, it is 0.5-10.

(A13) can be obtained by oxidizing (a0) with oxygen and / or ozone or hydroformylating with an oxo method to introduce a carbonyl group.
The introduction of the carbonyl group by oxidation can be carried out by a known method, for example, the method described in US Pat. No. 3,692,877. The introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, Macromolecules, Vol. 31, 5943 page.

(A14) can be obtained by secondary modification of (a13) with lactam or aminocarboxylic acid.
As lactam and aminocarboxylic acid, what was illustrated by (a12) is mentioned, The usage-amount is also the same.

Mn of polyolefin (a1) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably 1,000 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. ˜20,000, particularly preferably 2,500 to 10,000.
The acid value of (a1) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b), more preferably 4 to 100, particularly preferably. Is 5-50.

  Polyether diol (b1) and polyether diamine (b2) can be used as the hydrophilic polymer (b).

The polyether diol (b1) has a structure obtained by adding an alkylene oxide (hereinafter abbreviated as AO) (C2-12) to the diol (b01) or dihydric phenol (b02), for example, Examples thereof include those represented by the formula: H (OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} H.
Wherein, E ¹ represents the residue obtained by removing hydroxyl groups from (b01) or (bO2), A ¹ is C2-12 may include a halogen atom (preferably 2 to 8, more preferably 2 ~ 4) alkylene group; m and m 'represent an integer of 1 to 300, preferably 2 to 250, more preferably 5 to 200, particularly preferably 8 to 150, most preferably 10 to 100, m and m 'May be the same or different. In addition, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where these are composed of two or more oxyalkylene groups is a block form. , Random or a combination thereof.

As the diol (b01), C2-12 (preferably 2-10, more preferably 2-8) dihydric alcohol (aliphatic, alicyclic and araliphatic dihydric alcohol) and C1-12 tertiary. Examples thereof include amino group-containing diols.
Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,12-dodecanediol.
Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol, and 1,3-cyclopentanediol.
Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol and 1,4-bis (hydroxyethyl) benzene.

Tertiary amino group-containing diols include aliphatic or alicyclic primary monoamines (C1-12, preferably 2-10, more preferably 2-8) bishydroxyalkyl (alkyl group C1-12, preferably 2-10, more preferably 2-8) and bishydroxyalkyl (alkyl group C1-12) compounds of aromatic (aliphatic) primary monoamines (C6-12).
The monoamine bishydroxyalkylated product is obtained by reacting a known method, for example, reacting monoamine with C2-4 AO [ethylene oxide (hereinafter abbreviated as EO) propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] It can be easily obtained by reacting a monoamine with a C1-12 halogenated hydroxyalkyl (2-bromoethyl alcohol, 3-chloropropyl alcohol, etc.).

Aliphatic primary monoamines include methylamine, ethylamine, 1- and 2-propylamine, n- and i-amylamine, hexylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2- and 3- Examples include aminoheptane, heptylamine, nonylamine, decylamine, undecylamine, and dodecylamine.
Examples of the alicyclic primary monoamine include cyclopropylamine, cyclopentylamine, and cyclohexylamine.
Examples of the aromatic (aliphatic) primary monoamine include aniline and benzylamine.

  As the dihydric phenol (b02), C6-18 (preferably 8-18, more preferably 10-15), for example, monocyclic dihydric phenol (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenol (bisphenol A, Bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, dihydrokibiphenyl, etc.) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol, etc.).

  Of (b01) and (b02), from the viewpoint of compatibility, preferred are dihydric alcohols and dihydric phenols, more preferred are aliphatic dihydric alcohols and bisphenols, and particularly preferred are ethylene glycol and bisphenol A.

As AO to be subjected to addition reaction with diol (b01) or dihydric phenol (b02), C2-12 AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide And a mixture of two or more thereof), and other AOs and substituted AOs may be used in combination if necessary.
Examples of other AO and substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of each of the other AO and the substituted AO used is preferably 30% by weight or less, more preferably 0 or 25% by weight, particularly preferably 0 or 20% by weight based on the weight of the total AO from the viewpoint of hydrophilicity. % Or less.

When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Among AO, from the viewpoint of hydrophilicity, EO alone and a combination of EO and AO other than EO (block and / or random addition) are more preferable, and EO alone and a combination of EO and PO are particularly preferable. Is EO alone.
The number of moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles, more preferably 2 to 250 moles per hydroxyl group of (b01) or (b02), from the viewpoint of the volume resistivity value of the hydrophilic polymer (b). Preferably it is 10-100 mol.

The addition reaction of AO can be performed by a known method, for example, in the presence of an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) under the conditions of 100 to 200 ° C. and pressure of 0 to 0.5 MPaG.
The content of the oxyalkylene unit in the polyether diol (b1) is preferably from 5 to 99.8% by weight, more preferably from the viewpoint of the volume resistivity value of the hydrophilic polymer (b) based on the weight of (b1). Is 8 to 99.6% by weight, particularly preferably 10 to 98% by weight. Further, the content of the oxyethylene unit in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% from the viewpoint of the volume resistivity value of (b) based on the weight of the polyoxyalkylene chain. % By weight, particularly preferably 50 to 100% by weight, most preferably 60 to 100% by weight.

The polyether diamine (b2) has a structure in which the hydroxyl group of the polyether diol (b1) is modified to an amino group (primary or secondary amino group), for example, a general formula:
^{RNH-A 2 - (OA 1} ) m O-E 1 -O (A 1 O) m '-A 2 -NHR
The thing shown by is mentioned.
The symbol E ¹ in the formula represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ is a C2-12 (preferably 2-8, more preferably a halogen atom). 2-4) alkylene group; m and m ′ represent an integer of 1 to 300, preferably 2 to 250, more preferably 5 to 200, particularly preferably 8 to 150, most preferably 10 to 100, m and m ′ may be the same or different. A ² is C2~12 may include a halogen atom (preferably 2-8, more preferably 2-4) represents an alkylene group, may be the same or different and A ¹ and A ^2. R represents H or a C1-4 (preferably 1 or 2) alkyl group.
(B2) can be easily obtained by changing both terminal hydroxyl groups of (b1) to amino groups by a known method.
As a method of changing a hydroxyl group to an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group of (b1) to form an amino group [for example, (b1) and acrylonitrile And a method of hydrogenating the resulting cyanoethylated product], a method of reacting (b1) with an aminocarboxylic acid or lactam, and (b1)
And a method in which a halogenated amine is reacted under alkaline conditions.
As described above as (b), two or more kinds may be used in combination.

The volume resistivity value of the hydrophilic polymer (b) (value measured by the method described later in an atmosphere of 23 ° C. and 50% RH) is 10 ⁵ to 10 ¹¹ Ω · cm, preferably 10 ⁶ to 10 ¹⁰ Ω. · Cm, more preferably 10 ⁷ to 10 ⁹ Ω · cm. When the volume resistivity value is less than 10 ⁵ , the resin physical properties deteriorate, and when it exceeds 10 ¹¹ , the compatibility deteriorates.
Mn of (b) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with polyolefin (a). Most preferably, it is 1,200 to 8,000.

  In the block polymer (A), the block of the polyolefin (a) and the block of the hydrophilic polymer (b) have at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond and an imide bond. Among them, a polymer having a repeating unit represented by the following general formula (1) is preferable from the viewpoint of compatibility and transparency.

In the formula (1), n is an integer of 2 to 50 (preferably 3 to 40, more preferably 4 to 30); ^one of R ¹ and R ² is H and the other is H or a methyl group; y is 15 to 800 An integer of (preferably 20 to 500, more preferably 30 to 400); E ¹ is a residue obtained by removing a hydroxyl group from diol (b01) or dihydric phenol (b02); A ¹ may contain a halogen atom Good C2-12 (preferably 2-8, more preferably 2-4) alkylene group; m and m ′ are 1-300 (preferably 2-250, more preferably 5-200, particularly preferably 8-150). X and X ′ are groups selected from the following general formulas (2) and (3) and corresponding (2 ′) and (3 ′), that is, X is a general formula In the group represented by (2), X ′ is a general formula. It is a group represented by (2 ′), and the same relationship applies to general formulas (3) and (3 ′).

In the general formulas (2) and (3) and the corresponding formulas (2 ′) and (3 ′), R represents the above (b2)
Alkyl group the same as those stated H or C1 -4 (preferably 1 or 2) in, R ³
Alkyl of C1～11 (preferably 2 to 11, more preferably 5 to 11) a divalent hydrocarbon group, R ⁴ is H or C1-10 (preferably 1 to 8, more preferably 1 to 6) Group,
A ² is a C2-4 alkylene group; r is an integer of 1-20 (preferably 1-15, more preferably 1-10), u is 0 or 1; Q, Q ′, T and T ′ are Group represented by the following formula

In the general formulas (4) and (5) and the corresponding (4 ′) and (5 ′), R ⁵ is H or C1;
-10 (preferably 1-8, more preferably 1-6), R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H.

The polyether segment {(OA ¹ ) _m O—E ¹ —O (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) is the polyether diol (b1) or poly It is a structure derived from ether diamine (b2), and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

In the general formula (1), the block polymer in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) includes (a11) and / or (a12) (A1) obtained by polymerizing (b1) and (A2) obtained by polymerizing (a11) and / or (a12) and (b2).
(A1) includes (A11) in which (a11) and (b1) are combined, (A12) in which (a12) and (b1) are combined, and a mixture of (A11) and (A12). Similarly, (A2) includes (A21) in which (a11) and (b2) are combined, (A22) in which (a12) and (b2) are combined, and a mixture of (A21) and (A22). included.

(A1) is a known method, for example, a method in which (b1) is added to (a11) and / or (a12) and a polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure, or uniaxial Or it can manufacture by the method of superposing | polymerizing normally with 160-250 degreeC and residence time 0.1-20 minutes using a twin-screw extruder.
In the above polymerization reaction, a known catalyst, such as an antimony catalyst (antimony trioxide, etc.); a tin catalyst (monobutyltin oxide, etc.); a titanium catalyst (tetrabutyl titanate, etc.); a zirconium catalyst (tetrabutylzirconate, etc.); And acid metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate), zinc acetate, etc.]; and mixtures of two or more of these. Among these, a zirconium catalyst and a zirconium organic acid salt are preferable, and zirconyl acetate is more preferable.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (a11) and / or (a12) and (b1), Preferably it is 0.01 to 3%.

  Of (A1), (A12) may be reacted with (b1) after (a11) is secondarily modified with the above lactam or aminocarboxylic acid, or (a11) and lactam or aminocarboxylic acid may be reacted. The reaction may be carried out in the presence of (b1) followed by reaction with (b1).

(A2) is the same as (A1) except that the combination of (a11) and / or (a12) and (b1) in (A1) is replaced with the combination of (a11) and / or (a12) and (b2) It can be manufactured by the method.
Of (A2), (A22) may be produced by secondarily modifying (b2) with the lactam or aminocarboxylic acid and then reacting it with (a11).

In the general formula (1), the block polymer in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) includes (a13) (when r = 1) And / or (a14) (when r ≧ 2) and (b1) are subjected to a polymerization reaction (A3) and (a13) and / or (a14) and (b2) are subjected to a polymerization reaction (A4) obtained by the above.
(A3) includes (A31) in which (a13) and (b1) are combined, (A32) in which (a14) and (b1) are combined, and a mixture of (A31) and (A32). Similarly, (A4) includes (A41) in which (a13) and (b2) are combined, (A42) in which (a14) and (b2) are combined, and a mixture of (A41) and (A42). included.
(A3) and (A4) can be produced by the same method as (A1) and (A2).

  The amount of (b) constituting the block polymer (A) is preferably 20 to 90% by weight, more preferably 25 to 80% by weight based on the total weight of (a) and (b), from the viewpoint of compatibility. %, Particularly preferably 30 to 70% by weight.

  The Mn of the block polymer (A) is preferably from 2,000 to 60,000, more preferably from 5,000 to 40,000, particularly preferably from 8,000 to 30,000, from the viewpoint of coatability. If Mn is within this range, (A) will not bleed out from the hot melt adhesive over time.

In the structure of (A), the average number of repeating units (Nn) of the repeating unit of the polyolefin (a) block and the hydrophilic polymer (b) block is preferably 2 to 50 from the viewpoint of coatability. Preferably it is 3-40.
Nn can be determined by Mn and ¹ H-NMR analysis of (A).
For example, in the case of (A1) having a structure in which blocks of (a11) and (b1) are alternately and repeatedly bonded, 4.0 ^{1 to} 4.1 ppm ester bond {—C in ¹ H-NMR analysis A signal attributed to the proton of (C═O) —OCH ₂ —}, and 3.2-2
Since a signal attributed to 3.7 ppm polyethylene glycol protons can be observed, the ratio of these proton integral values can be determined, and Nn can be determined from this ratio and Mn.

The terminal of (A) is a carbonyl group, amino group and / or unmodified polyolefin terminal derived from (a) (polyolefin terminal not modified at all, ie, an alkyl group or alkenyl group), or a hydroxyl group derived from (b) And / or any amino group. Among these, a carbonyl group, an amino group, and a hydroxyl group are preferable as a terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

Diene copolymers (B) include butadiene rubber, isoprene rubber, natural rubber, butyl rubber, nitrile rubber, acrylic rubber, acrylonitrile-butadiene copolymer rubber (NBR), and styrene-butadiene-styrene block copolymer (SBS). Styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-isoprene-styrene block copolymer, styrene-butadiene random copolymer (SBR), part of the diene portion of a diene (co) polymer, or Fully hydrogenated hydride [styrene- (ethylene-propylene) -styrene block copolymer (SEPS; hydrogenated product of SIS), styrene- (ethylene-butylene) -styrene block copolymer (SEBS; SBS Hydrogenated product), styrene-ethylene- (ethylene -Propylene) -styrene block copolymer (SEEPS; hydrogenated styrene-butadiene-isoprene-styrene block copolymer), hydrogenated SBR, etc.], styrene-isobutylene-styrene block copolymer (SIBS) and the like. be able to.
Among these, SBS, SIS, SEPS, SEBS, SEEPS, and SIBS are preferable from the viewpoint of adhesive strength.
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 SEPS such as “Clayton D-1107” (styrene content 15% by weight) manufactured by Kraton Polymer Co., Ltd., SEBS “Septon 2063” (styrene content 13% by weight) manufactured by Kuraray Co., Ltd. As specific examples of the above, "Clayton G1651" (styrene content 33 wt%) manufactured by Kraton Polymer Co., Ltd., and as a specific example of SEEPS, "Septon 4033" (styrene content 30 wt%) manufactured by Kuraray Co., Ltd. As a specific example of SIBS, Kaneka Co., Ltd. “Sibstar 072T” (styrene content 23% by weight) is used. Respectively, and the like.

  As the tackifier resin (C), known tackifiers {adhesion techniques 20, (2), 13 (2000), etc.} can be used, and rosin, rosin derivatives (polymerized rosin, rosin ester, etc .; Mn200 to 1,000), terpene resins ((co) polymers such as α-pinene, β-pinene and / or limonene; Mn 300 to 1,200), coumarone-indene resins, petroleum resins (C5 fraction, C9 fraction, C5 / C9 fraction and / or (co) polymers such as dicyclopentadiene; Mn 300 to 1,200), styrene resins (styrene, α-methylstyrene and / or vinyl toluene (co) polymers, etc .; Mn200 ~ 3,000), acrylic resin {alkyl or alkenyl (meth) acrylate and / or (meth) acrylic acid (co) polymer, etc .; Mn200-3,000} Styrene-acrylic copolymer resins (Mn 200 to 5,000), xylene resins (xylene formaldehyde resins, etc .; Mn 300 to 3,000), phenol resins (phenol xylene formaldehyde resins, etc .; Mn 300 to 3,000) and these resins A hydride or the like is used. The copolymer constituting the tackifying resin includes a random, block and / or graft copolymer. Moreover, the (co) polymer polymerized in presence in the plasticizer (E) mentioned later is included.

  Of these, from the viewpoint of thermal stability and compatibility, hydrogenated terpene resins, hydrogenated petroleum resins, styrene resins, styrene-acrylic copolymer resins, and mixtures thereof are preferred, and C9 is more preferred. Distillate, hydrogenated (co) polymerized petroleum resin of C5 / C9 fraction, hydrogenated (co) polymerized petroleum resin of dicyclopentadiene, styrene polymer, styrene-alkenyl methacrylate copolymer and mixtures thereof It is.

The content (% by weight) of the block polymer (A) can be varied depending on the required performance based on the total weight of (A), (B) and (C), but sufficient hydrophilicity And from the viewpoint of imparting adhesiveness, it is preferably 2 to 80%, more preferably 5 to 70%.

  The content (% by weight) of the diene copolymer (B) is preferably 3% or more based on the total weight of (A), (B) and (C), more preferably 5%. % Or more. Moreover, from a viewpoint of coating property, 50% or less is preferable, More preferably, it is 40% or less.

  The content (% by weight) of the tackifier resin (C) is preferably 10% or more, more preferably from the viewpoint of improving the adhesive strength based on the total weight of (A), (B) and (C). 15% or more. Moreover, from a viewpoint of a soft improvement and a tack, 90% or less is preferable, More preferably, it is 80% or less.

  The hot melt adhesive of the present invention can contain a low molecular weight polyolefin (D) and a plasticizer (E) as necessary. When (D) is added, the compatibility of the resin is improved, and when (E) is added, the coatability is improved.

Examples of the low molecular weight polyolefin (D) include polypropylene, polyethylene, propylene and one or more other vinyl compounds [ethylene, α-olefin (C4-12, such as 1-butene, 4-methyl-1-pentene, etc.), acetic acid. Copolymers with vinyl, (meth) acrylic acid, etc.], graft modified products of these (co) polymers with (anhydrous) unsaturated carboxylic acids [above, eg (anhydrous) maleic acid], and these A blend of two or more types of copolymers or modified products may be mentioned.
Of these, polypropylene, polyethylene, propylene / ethylene copolymers and graft modified products of these (anhydrous) unsaturated carboxylic acids are preferable from the viewpoint of compatibility, and (anhydrous) unsaturation of polypropylene and polypropylene is more preferable. It is a graft modified product with carboxylic acid.

  The Mn of the low molecular weight polyolefin (D) is preferably 500 or more from the viewpoint of improving the cohesive strength of the hot melt adhesive, more preferably 800 or more, particularly preferably 1,000 or more, and the diene copolymer described above. From the viewpoint of improving the compatibility with the combined body (B), it is preferably 25,000 or less, more preferably 23,000 or less, and particularly preferably 20,000 or less.

  The amount of (D) used is usually 30% or less, preferably 0.1 to 25%, more preferably 0.5 to 20%, based on the total weight of (A), (B) and (C). .

As the plasticizer (E), a known plasticizer {adhesion technology 20, (2), 21 (2000), etc.] can be used, and paraffinic, naphthenic or aromatic process oil, liquid polybutene, liquid Liquid resins such as polybutadiene and liquid polyisoprene [weight average molecular weight (hereinafter abbreviated as Mw; measured by GPC method) = 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 a mixture of two or more thereof are used.
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 (E) used is usually 50% or less, preferably 1 to 45%, more preferably 5 to 40%, based on the total weight of (A), (B) and (C).

In the hot melt adhesive, alkali metal or alkaline earth metal salt (F), ionic liquid (G), and other resin additives (H) are necessary as long as the effects of the present invention are not impaired. You may contain the at least 1 sort (s) of additive chosen from the group which consists of.
The total amount of the additive based on the total weight of (A), (B) and (C) is usually 170% or less, preferably 0.001 to 100%.

Alkali metal or alkaline earth metal salt (F) includes alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids [C1-12 mono- and di- -Salts of carboxylic acids (formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), C1-20 sulfonic acids (methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.), thiocyanic acid, etc., And salts of inorganic acids [hydrohalic acid (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.].
Specific examples of (F) include acetates (lithium acetate, potassium acetate, etc.), halides [lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, excess Chlorates (lithium perchlorate, sodium perchlorate, potassium perchlorate, etc.)], potassium sulfate, potassium phosphate, potassium thiocyanate and the like.
Among (F), from the viewpoint of hydrophilicity, preferred are acetate (more preferred is potassium acetate) and halide [more preferred are lithium chloride, sodium chloride, potassium chloride, perchlorate (more preferred is perchlorate). Potassium chlorate)].
The amount of (F) used is preferably 5% or less based on the total weight of (A), (B) and (C), preferably from the viewpoint of giving a resin having a good appearance without being deposited on the resin surface. It is 0.001 to 5%, more preferably 0.01 to 3%, particularly preferably 0.1 to 2.5%, and most preferably 0.15 to 1.5%.
The method of containing (F) is preferably a method of dispersing in (A) in advance, and more preferably a method of containing (F) and dispersing and dissolving in the production of (A). There is no particular limitation on the timing of incorporating (F) during the production of (A), and it may be before, during or after the polymerization of the polyolefin block and the hydrophilic polymer block.

  The ionic liquid (G) is a compound other than the above (F), has a melting point of room temperature or lower, and at least one of cations or anions constituting (G) is an organic ion, and has an initial conductivity of 1 to 200 ms. / Mol (preferably 10-200 ms / cm), for example, room temperature molten salt described in WO95 / 15572.

  Examples of the cation constituting (G) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

Examples of the amidinium cation include imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.]; imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1, 2,3-trimethylimidazolium, etc.]; tetrahydropyrimidinium cation [1,3-dimethyl-1
, 4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5 6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, etc.]; and dihydropyrimidinium cation [1,3-dimethyl-1,4- Or 1,6-dihydropyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyrimidinium and the like].

Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-
Dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.]; guanidinium cation having an imidazolium skeleton [2-dimethylamino-1,3,4- Trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium Etc.]; Guanidinium cation having a tetrahydropyrimidinium skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4 -Trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino 1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium and the like]; and a guanidinium cation having a dihydropyrimidinium skeleton [2-dimethylamino-1,3,4-trimethyl] -1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3 -Dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimidinium, etc.].

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

The amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more.
Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (G), the following are mentioned as an organic acid and / or inorganic acid which comprise an anion.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid, and phosphate ester.
Examples of inorganic acids include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the above organic acids and inorganic acids, from the viewpoint of the initial conductivity of (G), a super strong acid or a super strong acid in which the Hammett acidity function (-H ₀ ) of the anion constituting (G) is 12 to 100 is preferable. These are acids that form anions other than the conjugated base, and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid) ions, and poly (n = 1 to 25). ) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [eg methane sulfonic acid, dodecane sulfonic acid etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (eg trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane) Sulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Of these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferred from the viewpoint of ease of synthesis.

Examples of proton acids used in combination with Lewis acids include hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity (G).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof.
Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (G).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, (G) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid made of a proton acid and a proton acid, and boron trifluoride and / or phosphorus pentafluoride.

The amount of (G) used is usually 10% or less based on the total weight of (A), (B) and (C), preferably from 0.001 to 5%, more preferably from the viewpoint of hydrophilicity and ion elution. 0.01 to 3%.
The method for adding (G) is also not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferably preliminarily dispersed in (A), and after the production of (A) (G) More preferably, it is added and dispersed in advance.

  Among the above additives, the other additive for resin (H) includes a colorant (H1), a filler (H2), a nucleating agent (H3), a lubricant (H4), a release agent (H5), and an antioxidant. (H6), a flame retardant (H7), an ultraviolet absorber (H8), and at least one selected from the group consisting of an antibacterial agent (H9).

Examples of the colorant (H1) include pigments and dyes.
Examples of pigments include inorganic pigments such as alumina white, graphite, titanium oxide (such as ultrafine titanium oxide), zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, resurge, lithopone, Barite, Cadmium red, Cadmium mercury red, Molybdenum red, Bengala, Red lead, Yellow lead, Barium yellow, Cadmium yellow, Strontium yellow, Titanium yellow, Aureolin, Titanium black, Chromium oxide green, Cobalt oxide, Cobalt green, Cobalt chromium Green, ultramarine blue, bitumen, cobalt blue, cerulean blue, manganese purple, cobalt purple, etc.], and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lakes, etc.).
Examples of dyes include azo, anthraquinone, indigoid, sulfide, triphenylmethane,
Examples include pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, nitroso and aniline dyes.

Examples of the filler (H2) include fibrous, granular, and plate-like fillers.
Examples of the fibrous filler include glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, aramid fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, and the like. Of these, glass fibers and carbon fibers are preferable from the viewpoint of the mechanical strength of the molded product.
As granular fillers, carbon black, silica, quartz powder, glass beads, silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silica powder, etc.), metal oxides (iron oxide, titanium oxide, Zinc oxide, alumina, etc.), metal carbonates (calcium carbonate, magnesium carbonate, etc.), metal (sulfur) sulfates (calcium sulfate, barium sulfate, aluminum sulfate, calcium sulfite, etc.), metal sulfides (molybdenum disulfide) Etc.), silicon carbide, silicon nitride, boron nitride and various metal (magnesium, silicon, aluminum, titanium, copper, silver, gold, etc.) powders.
Examples of the plate-like filler include mica, glass flakes, and various metal (aluminum, copper, silver, gold, etc.) foils.
These fillers may be used alone or in combination of two or more.
Of the above fillers, a fibrous filler is preferable from the viewpoint of the mechanical strength of the molded product, and a glass fiber is more preferable.

    Examples of the nucleating agent (H3) include polyvalent organic acids and / or metal salts thereof, aryl phosphate compounds, cyclic polyvalent metal aryl phosphate compounds, and dibenzylidene sorbitol compounds.

  Examples of polyvalent organic acids and / or metal salts thereof include malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, Cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid Acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, 4-t-butylan acid Carboxylic acids such as perfume acid, salicylic acid, phthalic acid, trimellitic acid, pyromellitic acid (excluding aliphatic monocarboxylic acids) or alkali metals such as lithium, sodium, potassium, magnesium, calcium, strontium, barium And alkaline earth metal, zinc or aluminum salts.

Examples of the aryl phosphate compound include metal salts of the following compounds.
Bis (4-t-butylphenyl) phosphate, bis (4-cumylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, 2,2′-methylene-bis ( 4-cumyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, 2,2′-methylene-bis (4-ethyl-6- t-butylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-methylphenyl) phosphate, 2,2′-methylene-bis (4,6-di-ethylphenyl) phosphate, 2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, 2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate 2,2′-ethylidene-bis (4-s-butyl-6-tert-butylphenyl) phosphate, 2,2′-butylidene-bis (4,6-di-methylphenyl) phosphate, 2,2′-butylidene -Bis (4,6-di-t-butylphenyl) phosphate, 2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, 2,2'-t-octylmethylene-bis (4,6-di-t-butylphenyl) phosphate, 4,4'-dimethyl-6,6'-di-t-butyl-2,2
Salts of alkali metals (e.g. lithium, sodium, potassium) such as' -biphenyl) phosphate, mono- and bis- (4-tert-butylphenyl) phosphate, dihydrooxy- (4-tert-butylphenyl) phosphate, dihydrooxy -Salts of aluminum, calcium and zinc such as bis (4-t-butylphenyl) phosphate and tris (4-t-butylphenyl) phosphate.

  Examples of the cyclic polyvalent metal aryl phosphate compound include bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-methylene-bis (4-methyl-). 6-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-methyl-6-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-ethyl-6-t-) Butylphenyl) phosphate], bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], bis [2,2′-thiobis (4-t-octylphenyl) phosphate], bis [ 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], bis [(4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) ) Phosphate], bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) Phosphate], tris [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], dihydroxy-2,2′-methylene-bis (4,6-di-t-butyl) Phenyl) phosphate, dihydrooxy-2,2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate, dihydrooxy-bis [2,2′-methylene-bis (4,6-di-t) -Butylphenyl) phosphate], dihydrooxy-2,2'-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate, dihydrooxy-2,2'-ethyl Den-bis (4,6-di-t-butylphenyl) phosphate, hydroxy-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], hydroxy-bis [2, 2′-methylene-bis (4-cumyl-6-tert-butylphenyl) phosphate], bis [2,2′-methylene-bis (4,6-di-tert-butylphenyl) phosphate], hydroxy-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxy-bis [2,2′-ethylidene-bis (4,6-di-tert-butylphenyl) phosphate] And alkaline earth metals (for example, calcium and barium), aluminum, titanium, magnesium, zinc, oxyzirconium salts, and the like.

Dibenzylidene sorbitol compounds include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene Sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-bis (p-methylbenzylidene) sorbitol, 1,3,2,4-bis (p- Ethylbenzylidene) sorbitol, 1,3,2,4-bis (pn-propylbenzyl) Den) sorbitol, 1,3,2,4-bis (pi-propylbenzylidene) sorbitol, 1,3,2,4-bis (pn-butylbenzylidene) sorbitol, 1,3,2,4- Bis (ps-butylbenzylidene) sorbitol, 1,3,2,4-bis (pt-butylbenzylidene) sorbitol, 1,3- (2 ', 4'-dimethylbenzylidene) -2,4-benzylidene Sorbitol, 1,3-benzylidene-2,4- (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2 4-bis (3 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-bis (p-methoxybenzylidene) sorbitol, 1,3,2,4-bis (p-ethoxybenzene) Benzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol,
3-p-chlorobenzylidene-2, 4-benzylidene sorbitol, 1, 3-p-chlorobenzylidene-2, 4-p-methylbenzylidene sorbitol, 1, 3-p-chlorobenzylidene-2, 4-p-ethyl Benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, and 1,3,2,4- Bis (p-chlorobenzylidene) sorbitol and the like can be mentioned.

  Examples of the lubricant (H4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), and the like.

  Examples of the release agent (H5) include lower alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (such as hardened castor oil), glycol esters of fatty acids (such as ethylene glycol monostearate), and liquid paraffin. And hydrogenated products of those having unsaturated double bonds that can be hydrogenated.

  Antioxidants (H6) include phenolic [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.], bisphenol [2,2′-methylenebis (4-methyl- 6-t-butylphenol), 4,4′-butylidenebis (3-methyl) -6-t-butylphenol, 4,4′-thiobis (3-methyl) -6-t-butylphenol], polycyclic phenol [1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane, pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( , 5-di-tert-butyl-4-hydroxyphenyl) propionate]; sulfur-based [dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3 ′ -Thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl β, β'-thiodibutyrate, dilauryl sulfide, etc.]; phosphorous [triphenyl phosphite, triisodecyl phosphite, diphenyl iso Decyl phosphite, phenyl diisodecyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4 ′ -Butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phos Ite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentane tetrayl bis (2 , 4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, etc.]; amine-based [octylated diphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine N, N-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine, phenothiazine, etc.) Etc.

  Examples of the flame retardant (H7) include organic flame retardants [nitrogen-containing [urea compounds, guanidine compounds, triazine compounds (melamine, guanamine, etc.) salts (inorganic acid salts, cyanurates, isocyanurates, etc.), etc.] ], Sulfur-containing [sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid and their salts, esters, amides, etc.], silicon-containing (polyorganosiloxane, etc.), phosphorus-containing [phosphoric acid ester (triester Etc.)], and inorganic flame retardants [antimony trioxide, magnesium hydroxide, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, ammonium polyphosphate, etc.].

  Examples of the ultraviolet absorber (H8) include benzotriazoles [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, etc.], Benzophenone [2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, etc.], salicylate [phenyl salicylate, ethylene glycol monosalicylate, etc.], acrylate [2-ethylhexyl- 2-cyano-3,3′1-diphenyl acrylate, etc.].

  Antibacterial agents (H9) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenols (2,4,6-tribromophenol sodium salt, etc.), organic iodine (4-chlorophenyl-3-iodopropargyl formal) ), Nitrile (2,4,5,6-tetrachloroisophthalonitrile, etc.), thiocyano (methylene bisthocyanocyanate, etc.), N-haloalkylthioimide (N-tetrachloroethyl-thio-tetrahydrophthalimide, etc.), copper agent (Such as 8-oxyquinoline copper), benzimidazole (such as 2-4-thiazolylbenzimidazole), benzothiazole (such as 2-thiocyanomethylthiobenzothiazole), trihaloallyl (3-bromo-2,3-diiodo-2 -Propenyl ethyl carbonate, etc. , Triazole (such as azaconazole), organic nitrogen sulfur compound (such as Suraoff 39), quaternary ammonium compound (such as trimethoxysilyl-propyloctadecyl ammonium chloride), pyridine compound (2,3,5,6-cytochloro-4- ( Methylsulfonyl) -pyridine) and the like.

The total amount of (H) used is usually 180% or less, preferably 0.1 to 100%, based on the total weight of (A), (B) and (C). The amount of each (H) used is based on the total weight of (A), (B) and (C), (H1) is usually 5% or less, preferably 0.1-3%; (H2) is usually 150% or less, preferably 5 to 100%; (H3) is usually 20% or less, preferably 1 to 10%; (H4) is usually 20% or less, preferably 1 to 10%; (H5) is usually 10% Or less, preferably 0.1 to 5%; (H6) is usually 5% or less, preferably 0.1 to 3%; (H7) is usually 20% or less, preferably 1 to 10%; (H8) is usually 5% or less, preferably 0.1 to 3%; (H9) is usually 3% or less, preferably 0.05 to 1%.
Each of the above (H) s may be used alone or in combination of two or more. Moreover, when an additive is the same and overlaps between said (H1)-(H9), it does not use the quantity which shows each addition effect irrespective of other effects, but the usage-amount according to a use purpose Shall be adjusted.

The water absorption rate at 25 ° C. of the hot melt adhesive of the present invention is preferably 2 to 100%, more preferably 3 to 90%, and particularly preferably 5 to 80%. If the water absorption is 2 or more, the hydrophilicity of the hot melt adhesive is sufficient, and if it is 100% or less, good adhesive strength can be obtained. The method for measuring the water absorption rate is as follows.
(Measurement method): About 10 g of hot-melt adhesive is sandwiched between release papers, heated and press-molded to form a sheet of 1 mm thickness, cut into a 30 mm × 30 mm × 1 mm sheet sample, and weight (X) is measured with an electronic balance. Measure to 4 digits after the decimal point. Subsequently, it is immersed in water adjusted to 25 ° C. for 8 hours, and after removing water droplets on the surface, the weight (Y) is measured in the same manner. Calculate the water absorption rate by the following formula.

Water absorption (%) = [{(Y) − (X)} / (X)] × 100

The melt viscosity at 160 ° C. of the hot melt adhesive of the present invention is preferably 1 to 100 Pa · s, more preferably 1.5 to 90 Pa · s, and particularly preferably 2 to 80 Pa · s. If the 160 ° C. melt viscosity is 1 Pa · s or more, the cohesive force is sufficient, and if it is 100 Pa · s or less, good coatability is obtained. The melt viscosity at 160 ° C. is measured by the following method.
(Measuring method): 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, temperature-controlled at 160 ° C. for 20 minutes in an oil bath, and an SB type viscometer (JIS k7117-1987, SB4 spindle, For example, a BL type viscometer manufactured by Toki Sangyo Co., Ltd. and a No. 4 rotor) are set and the temperature is further adjusted for 10 minutes, and then the rotor is rotated to read the melt viscosity after 10 minutes.

Although it does not specifically limit as a manufacturing method of the hot-melt-adhesive agent of this invention, For example, (D), (E), ((1) (A), (B) and (C), or these as needed, for example. F), (G) and / or (H) are added [(F) and (G) may be previously contained in (A) from the viewpoint of effective dispersion as described above. ] A method of melting and mixing; (2) A method of adding an organic solvent (toluene, xylene, etc.) and dissolving each component by heating and mixing them uniformly, and then distilling off the solvent; The method (1) is industrially preferable.
As the mixing device, a heat-melt kneader can be used. 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 single screw, etc. Or a multi-screw extruder, a mixer, etc. can be mentioned. The mixing temperature is usually 100 ° C. to 250 ° C., and it is preferably performed in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration.

  The adhesive body of the present invention is obtained by applying the above hot melt adhesive to an adherend. As an adherend, for example, various plastic molded articles, rubber, paper (tissue etc.), cloth (cotton, silk etc.), metal, wood, glass, mortar concrete, etc. can be applied, but polyolefin ( (Polyethylene, polypropylene, etc.) It is suitable for bonding resin-based molded products to each other or the above-mentioned other adherends.

As a method of applying the hot melt adhesive of the present invention to an adherend, (1) a method of melting and coating the adherend, (2) a hot melt adhesive formed into a film or the like The method of heating after arrange | positioning between is mentioned.
The coating method may be any known coating method such as spiral coating, spray coating, roll coating, slot coat coating, control seam coating and bead coating, but is not limited thereto. is not. The coating amount (g / m ² ) is preferably 0.1 or more, more preferably 1 or more from the viewpoint of adhesiveness in surface coating. Moreover, 100 or less is preferable from a viewpoint of see-through property, More preferably, it is 50 or less.
The coating amount (g / m) in the wire coating is preferably 0.005 or more, more preferably 0.01 or more, from the viewpoint of adhesiveness. Moreover, 1 or less is preferable from a flexible viewpoint, More preferably, it is 0.5 or less.

In the method (2), the film-like thickness (μm) is preferably 1 or more, more preferably 5 or more, from the viewpoint of adhesiveness. Moreover, 500 or less is preferable from a flexible viewpoint, More preferably, it is 300 or less.
When applied to an adherend, the melting temperature (° C.) of the adhesive of the present invention is preferably 80 or more, more preferably 100 or more, from the viewpoint of coatability. Further, from the viewpoint of thermal stability, it is preferably 220 or less, more preferably 200 or less.

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

Production Example 1
Thermal degradation method [Density 0.90 at 23 ° C. (Unit: g / cm ³ ;
MFR 6.0 g / 10 min ethylene / propylene random copolymer (ethylene content 2%)
Low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89, 7.1 double bond amount per 1,000 C, (Average number of double bonds per molecule 1.8, content of polyolefin capable of modification at both ends 90%) 90 parts, 10 parts maleic anhydride and 30 parts xylene, mixed in nitrogen gas atmosphere (sealed) The mixture was melted at 200 ° C. and reacted at 200 ° C. for 20 hours.
Thereafter, excess maleic anhydride and xylene were distilled off at 200 ° C. under reduced pressure for 3 hours to obtain acid-modified polypropylene (a111). The acid value of (a111) was 27.2, and Mn was 3,700.

Production Example 2
Low molecular weight polypropylene (Mn 10, 0) obtained by the thermal degradation method [polypropylene having a density of 0.90 at 23 ° C. and an MFR of 10 (g / 10 min) at 410 ± 0.1 ° C.]
00, density 0.89, 1.3 double bonds per 1,000 C, average number of double bonds per molecule 1.8, content of polyolefin capable of modification at both ends 90 wt%) 94 Parts, 6 parts of maleic anhydride and 30 parts of xylene were mixed, and then the acid-modified polypropylene (a112) was obtained in the same manner as in Production Example 1. The acid value of (a112) was 5.0, and Mn was 10,000.

Production Example 3
66 parts of acid-modified polypropylene (a111) and 34 parts of 12-aminododecanoic acid are melted at 200 ° C. in a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under a reduced pressure of 10 mmHg or less to give acid-modified polypropylene (a121). Got.
The acid value of (a121) was 17.7, and Mn was 5,700.

Production Example 4
90 parts of low molecular weight polypropylene and 0.5 part of cobalt hydroxide used in Production Example 2 are put into a pressure resistant reactor, melted at 150 ° C., and a mixed gas of hydrogen and carbon monoxide 1: 1 is blown to 100 atm. , And reacted at 150 ° C. for 5 hours. Thereafter, the pressure was returned to normal pressure, Tollens reagent (silver nitrate-ammonia aqueous solution) was added, and the mixture was reacted at 150 ° C. for 3 hours to obtain acid-modified polypropylene (a131). The acid value of (a131) was 41.6, and Mn was 2,600.

Production Example 5
95 parts of acid-modified polypropylene (a111) and 40 parts of bis (2-aminoethyl) ether were melted at 180 ° C. in a nitrogen gas atmosphere and reacted at the same temperature for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (a141) having an amino group. The amine value of (a141) is 26.2, Mn
Was 3,800.

Production Example 6
In a stainless steel autoclave, 60 parts of acid-modified polypropylene (a121), polyethylene glycol (b11) (Mn 3,200, volume resistivity 3 × 10 ⁸ Ω · cm) 3
3 parts, 7 parts sodium dodecylbenzenesulfonate, antioxidant [Irganox 10
10, manufactured by Ciba Specialty Chemicals, the same applies hereinafter. 0.3 parts and 0.5 parts of zinc acetate were added, and polymerization was carried out for 4 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a block polymer (A11).
The Mn of (A11) was 28,000. The average number of repetitions Nn of (A11) determined from this Mn and ¹ H-NMR analysis was 3.4.

Production Example 7
In a stainless steel autoclave, 71 parts of acid-modified polypropylene (a112), 2 parts of 12-aminododecanoic acid, α, ω-diaminopolyethylene glycol (b21) (Mn 8,000, volume resistivity 3 × 10 ⁷ Ω · cm) 25 parts, 0.5 part of lithium trifluoromethanesulfonate, 0.3 part of antioxidant and 0.5 part of zirconyl acetate are added and polymerized for 5 hours at 230 ° C. under a reduced pressure of 1 mmHg or less to obtain a viscous polymer. Got. Thereafter, a block polymer (A21) was obtained in the same manner as in Production Example 6.
The Mn of (A21) was 36,000. The average number of repetitions Nn of (A21) determined from this Mn and ¹ H-NMR analysis was 2.0.

Production Example 8
In a stainless steel autoclave, 31 parts of acid-modified polypropylene (a131), polyethylene glycol (b12) (Mn6,000, volume resistivity 2 × 10 ⁵ Ω · cm) 6
9 parts, 0.5 parts of potassium acetate, 0.3 parts of antioxidant and 0.5 parts of zirconyl acetate were added and polymerized for 4 hours under reduced pressure at 230 ° C. and 1 mmHg or less to obtain a viscous polymer. . Thereafter, a block polymer (A31) was obtained in the same manner as in Production Example 6.
The Mn of (A31) was 59,000. The average number of repetitions Nn of (A31) determined from this Mn and ¹ H-NMR analysis was 6.6.

Production Example 9
In a stainless steel autoclave, 71 parts of acid-modified polypropylene (a112), 25 parts of α, ω-diaminopolyethylene glycol (b21) (Mn8,000, volume resistivity 3 × 10 ⁷ Ω · cm), lithium trifluoromethanesulfonate 0.5 part, 0.3 part of antioxidant and 0.5 part of zirconyl acetate were added, and polymerization was performed at 230 ° C. under reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. Thereafter, a block polymer (A41) was obtained in the same manner as in Production Example 6. The Mn of (A41) was 33,000. The average number of repetitions Nn of (A41) determined from this Mn and ¹ H-NMR analysis was 1.9.

Production Example 10
Stainless steel autoclave, amino-modified polypropylene (a141) 71 parts, α, ω-diepoxypolyethylene glycol (b31) (Mn1,700, volume resistivity 2 × 10 ⁷ Ω · cm) 29 parts, screw (Trifluoromethylsulfonyl) lithium imidoate (2.0 parts), antioxidant (0.3 parts), and zinc oxide (0.5 parts) were charged and polymerized for 4 hours under stirring at 230 ° C. under a reduced pressure of 1 mmHg or less. A viscous polymer was obtained. Thereafter, a block polymer (A51) was obtained in the same manner as in Production Example 6. The Mn of (A51) was 12,000. The average number of repetitions Nn of (A51) determined from this Mn and ¹ H-NMR analysis was 2.2.

  In accordance with the formulation (parts) shown in Table 1, each component was put into a stirrable stainless steel pressure reaction vessel, and the inside of the vessel was purged with nitrogen, and then the temperature was raised to 160 ° C. by sealing, and stirred for 4 hours. By carrying out melt mixing, the hot melt adhesive of the present invention and a comparative hot melt adhesive were obtained.

Explanation of symbols (B1): styrene-butadiene-styrene block copolymer [trade name: TR-2000
, Manufactured by JSR Co., Ltd., styrene content 40% by weight; MFR: 3 (230 ° C., 2.1
6kg)]
(B2): Styrene- (ethylene-propylene) -styrene block copolymer [trade name:
Septon 2063, manufactured by Kuraray Co., Ltd., styrene content 13% by weight; MFR: 7 (2
30 ° C., 2.16 kg)]
(C1): Hydrogenated product of dicyclopentadiene copolymerized petroleum resin [trade name: Escorez E-
5600, manufactured by ExxonMobil Corporation, softening point: 100 ° C]
(C2): Hydrogenated copolymer petroleum resin of C9 fraction [trade name: Alcon P-100, Arakawa Chemical
Made by Gaku Kogyo Co., Ltd., softening point: 100 ° C]
(D1): Low molecular weight polyolefin [Brand name: Biscol 660P, Sanyo Chemical Industries, Ltd.
Manufactured, softening point: 145 ° C]
(D2): Carboxylic anhydride-modified low molecular weight polyolefin [trade name: Umex 1010
Manufactured by Sanyo Chemical Industries, softening point: 145 ° C.]
(E1): Paraffinic process oil [trade name: Diana Process Oil PW-90,
Idemitsu Kosan Co., Ltd.]
(E2): Naphthenic process oil [trade name: Diana process oil NS-100,
Idemitsu Kosan Co., Ltd.]
(H1): Phenolic antioxidant [trade name: Irganox 1010, Ciba Specialty
Made by Tea Chemicals Co., Ltd.]
(H2): Phosphorous antioxidant [trade name: ADK STAB 2112, manufactured by Asahi Denka Kogyo Co., Ltd.]

About the obtained hot-melt-adhesive, the adhesive evaluation by the measurement of T-type peeling strength, and thermal stability evaluation were implemented. The measuring method is as follows.
(1) T-type Peel Strength The hot melt adhesive of the present invention and the comparative were applied in a bead shape with a width of 25 mm to a polypropylene nonwoven fabric having a length of 100 mm × width of 25 mm × thickness of 100 μm (application temperature of 160 ° C., application amount of 0.2 g / m), and a cotton cloth of the same size was pasted and allowed to stand in an atmosphere at 25 ° C. for 24 hours was used as a test piece for T-type peel strength evaluation.
(I) Dry (Dry) State Using the tensile tester (Autograph AGS-500B (manufactured by Shimadzu Corporation)), the test piece was measured for peel strength at a tensile speed of 300 mm / min. Was T-type peel strength (dry) (N / 25 mm).
(Ii) Wet state in water (wet) The above test piece is set in a tensile tester (Autograph AGS-500B (manufactured by Shimadzu Corporation)) and water is dropped on the cotton cloth with a spoid (about 3 (~ 5 drops), the entire area where the hot melt adhesive was applied was wetted with water, and after 30 seconds, the peel strength was measured at a tensile rate of 300 mm / min, and the maximum value was defined as T-type peel strength (wet). N / 25m
m).

  Table 2 shows the physical properties and performance evaluation results of the hot melt adhesives of the present invention (Examples 1 to 8) and comparative hot melt adhesives (Comparative Examples 1 to 3).

  As is apparent from Table 2, the hydrophilic hot melt adhesives (Examples 1 to 8) of the present invention are more hydrophilic (water absorption) than the comparative hot melt adhesives (Comparative Examples 1 to 3). In addition to having good adhesive strength when wet with water, the hydrophilic component is a polymer, so that there is no decrease in hydrophilic performance due to bleeding out or the like.

  Since the hot melt adhesive of the present invention has excellent hydrophilicity, adhesive properties and thermal stability, various plastic molded products, rubber, paper (tissue etc.), cloth (cotton, silk etc.), metal, wood, It can be applied to glass, mortar concrete, etc., but is particularly suitable for bonding polyolefin (polyethylene, polypropylene, etc.) resin molded products that are difficult to adhere to each other or these and other adherends. In addition, since the adhesive strength can be ensured even when the surface is wet, it is also suitable for bonding water-based products such as bath mats, bonding sanitary materials (disposable disposable diapers, sanitary products, etc.) and bonding raindrops. be able to.

Claims (4)

The block of the polyolefin (a) and the block of the hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm are composed of an ester bond, an amide bond, an ether bond and an imide bond. A hydrophilic hot melt adhesive comprising a block polymer (A), a diene copolymer (B), and a tackifier resin (C) having a structure in which they are alternately and alternately bonded through at least one bond selected from the group. The hydrophilic hot melt adhesive according to claim 1, wherein (A) is a block polymer (A1) having a repeating unit represented by the following general formula (1).

[In the formula (1), n is an integer of 2 to 50, ^one of R ¹ and R ² is H and the other is H or a methyl group, y is an integer of 15 to 800, E ¹ is a hydroxyl group from a diol or a dihydric phenol. , A ¹ is an alkylene group having 2 to 12 carbon atoms which may contain a halogen atom, m and m ′ are integers of 1 to 300, and X and X ′ are the general formulas (2) and (3 ) And a corresponding group selected from (2 ′) and (3 ′) (where X ′ is a symmetrical group corresponding to X); (2), (3) and corresponding (2 ′), (3 ') In the formula, R is H or an alkyl group having 1 to 4 carbon atoms, R ³ is a divalent hydrocarbon group having 1 to 11 carbon atoms, R ⁴ is H or an alkyl group having 1 to 10 carbon atoms, A ² Is an alkylene group having 2 to 12 carbon atoms which may contain a halogen atom, r is an integer of 1 to 20, u is 0 or 1, Q, T, Q ′ and T ′ are represented by the general formulas (4), (5 ) Fine corresponding (4 '), (5') a group represented by; general formula (4), (5) and the corresponding (4 '), (5') wherein, R ⁵ is H or a carbon number 1 to 10 alkyl groups, R ⁶ is H or a methyl group, t is 1 when R ⁶ is a methyl group, and 0 when H is H. ] The hydrophilic hot melt adhesive according to claim 1 or 2, further comprising a low molecular weight polyolefin (D) and a plasticizer (E). The adhesive body adhere | attached with the hydrophilic hot-melt-adhesive in any one of Claims 1-3.