JP5165209B2 - Hot melt adhesive - Google Patents

Description

  The present invention relates to a hot melt adhesive. More specifically, it has excellent adhesive properties between thermoplastic substrates made of thermoplastic resins, particularly low-polarity polyolefin resins, or between these plastic substrates and other highly polar adherends (for example, polycarbonate, polyester, ABS, etc.). The present invention relates to a hot melt adhesive.

  Conventionally, as a hot melt adhesive used for adhesion of polyolefin resin films, nonwoven fabrics, resin molded articles (including adhesion between polyolefin resins and between polyolefin resins and other resins), styrene-ethylene-propylene- Known are those obtained by adding a liquid plasticizer such as a tackifying resin component and process oil to a styrene block copolymer rubber or a styrene-butadiene-styrene block copolymer rubber (see, for example, Patent Documents 1 and 2). .

Japanese Patent Laid-Open No. 3-160083 JP-A-8-60121

However, when the above is used as a hot melt adhesive, the fluidity of the adhesive (hereinafter abbreviated as fluidity) and the cohesive force (hereinafter abbreviated as agglomeration force) and holding power (hereinafter abbreviated as agglomeration force) The holding power and the abbreviation) cannot be made compatible, and the adhesion between the polyolefin resin molded article and the adherend is not satisfactory.
An object of the present invention is to provide a hot melt adhesive that can achieve both fluidity, cohesion and holding power, and is excellent in adhesion between a polyolefin resin molded article and an adherend.

  As a result of intensive studies to solve these problems, the present inventors have reached the present invention. That is, this invention acid-modifies the polyolefin (A) which has 15-70 mol% of C4-C12 alpha olefins (a), 30-85 mol% of propylene, and 0-1 mol% of ethylene as a structural unit. It is a hot melt adhesive comprising an acid-modified polyolefin (B) having a melting point of 50 to 120 ° C.

The hot melt adhesive of the present invention has the following effects.
(1) Excellent fluidity and excellent cohesion and holding power.
(2) Excellent adhesion between the polyolefin resin molded article and the adherend.

The hot-melt adhesive of the present invention comprises a polyolefin (A) having 15 to 70 mol% of an α-olefin (a) having 4 to 12 carbon atoms, 30 to 85 mol% of propylene and 0 to 1 mol% of ethylene as structural units. An acid-modified polyolefin (B) having a melting point of 40 to 120 ° C. is formed by acid modification.
(A) is an α-olefin having 4 to 12 carbon atoms (hereinafter abbreviated as C), and when C exceeds 12, the adhesive strength is deteriorated.
Examples of (a) include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene.
Of these, 1-hexene and 1-octene are preferable from the viewpoint of adhesion, and 1-butene, 1-pentene and 4-methyl-1-pentene are more preferable, and 1-butene is particularly preferable. .

The proportion of (a) constituting (A) is 15 to 70 mol%, preferably 17 to 60 mol%, more preferably 20 to 50 mol%. When the proportion of (a) is less than 15 mol%, the fluidity and adhesive strength are deteriorated, and when it exceeds 70 mol%, the holding power is deteriorated.
The proportion of propylene constituting (A) is 30 to 85 mol%, preferably 40 to 80 mol%, more preferably 50 to 75 mol%. When the proportion of propylene is less than 30 mol%, the holding power is deteriorated, and when it exceeds 85 mol%, the fluidity and adhesive force are deteriorated.
The proportion of ethylene in (A) is 0 to 1 mol%, preferably 0 to 0.5 mol%, more preferably 0 to 0.1 mol%. When the ratio of ethylene exceeds 1 mol%, fluidity is deteriorated.

The number average molecular weight (hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC) method) of (A) is preferably 500 to 40,000, more preferably 1 from the viewpoint of adhesive strength and fluidity. , 3,000 to 35,000, particularly preferably 1,500 to 30,000. The measurement conditions for GPC are as follows, and so on.
(GPC measurement conditions)
[1] Apparatus: Waters 150-CV [manufactured by Waters Co., Ltd.]
[2] Column: PLgel 10. MIXED-B [Polymer Laboratory
Product]
[3] Eluent: o-dichlorobenzene [4] Reference material: polystyrene [5] Injection conditions: sample concentration 3 mg / ml, column temperature 135 ° C.

The amount of double bonds per 1,000 carbon atoms in the molecular end and / or in the molecule (A) is preferably 0.2 to 10 from the viewpoint of ease of modification and adhesive strength of (A), More preferably, it is 0.3-6, and particularly preferably 0.5-5. The double bond content here can be calculated from the peak derived from the double bond between 4.5 and 6.0 ppm in the spectrum obtained from ¹ H-NMR (nuclear magnetic resonance) spectroscopy.

The production method of (A) includes various production methods such as a thermal degradation method (for example, those described in JP-B 43-9368, JP-B 44-29742 and JP-B 6-70094) and Polymerization methods (for example, those described in JP-A-59-206409 and JP-A-55-135102) are included. Among these, the thermal degradation method is preferable from the viewpoint of adhesive strength.
In the thermal degradation method, Mn is usually 8,000 to 500,000 [from (A) easy modification and industrial viewpoint, preferably 10,000 to 300,000, more preferably 15,000 to 150,000] high molecular weight polyolefin (A0) continuously under an inert gas (such as nitrogen) and (1) in the absence of organic peroxide, usually at 300 to 450 ° C. for 0.5 to 10 hours. And (2) a method of continuously thermally degrading at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide. Among these, the method (1) is preferable from the viewpoint of adhesion.

The acid-modified polyolefin (B) in the present invention is obtained by reacting the polyolefin (A) with an unsaturated polycarboxylic acid or derivative (b) in the presence or absence of the radical initiator (c).
Among (b), unsaturated polycarboxylic acids include dicarboxylic acids [for example, aliphatic (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid), and alicyclic (C8-24). , Eg, cyclohexene dicarboxylic acid and cycloheptene dicarboxylic acid)]; trivalent to tetravalent or higher polycarboxylic acids [eg, aliphatic polycarboxylic acids (C5-24, such as aconitic acid)]; and two or more thereof Of the mixture.

Among the unsaturated polycarboxylic acid derivatives in (b), for example, the unsaturated polycarboxylic acid anhydrides [C4-24, such as maleic anhydride, itaconic anhydride, citraconic anhydride and aconitic anhydride], alkyl (C1-18) esters [C5-60, such as maleic acid mono- and dimethyl esters, fumaric acid mono- and diethyl esters, itaconic acid mono- and di-t-butyl esters, mesaconic acid monodecyl esters and cycloheptene dicarboxylic acids Acid didodecyl ester], amide [C4-60, such as maleic acid monoamide, maleic acid monomethylamide, maleic acid diamide, maleic acid dimethylamide, fumaric acid monoethylamide, itaconic acid di-t-butylamide, mesaconic acid monodecylamide And cycloheptene Carboxylic acid didodecyl amide] and imides [C4～24, such as maleic acid imide, itaconic acid imides, citraconic imide and cycloheptenylidenephenyl braille acid imides, and mixtures of two or more thereof.
Among these, unsaturated dicarboxylic acid and its anhydride are preferable, and maleic anhydride is more preferable from the viewpoints of adhesive strength, holding power, and industry.

  The reaction molar ratio of (A) and (b) is preferably 99/1 to 2/98, more preferably 95/5 to 3/97, and particularly preferably 80/20 from the viewpoints of cohesive strength, holding power and adhesive strength. ~ 4/96. Unreacted (b) in (B) is preferably 10% by weight or less, more preferably 0 to 1% by weight, and particularly preferably 0 to 0.1% by weight from the viewpoint of adhesive strength. ]

(A) and (b) can be reacted in the presence or absence of the radical initiator (c), but in the presence of (C) from the viewpoint of adhesive strength. preferable.
Examples of (c) include azo compounds (for example, azobisisobutyronitrile and azobisisovaleronitrile) and peroxides [monofunctional (having one peroxide group in the molecule)] [for example, benzoyl peroxide, di- -T-butyl peroxide, lauroyl peroxide and dicumyl peroxide] and polyfunctional (having two or more peroxide groups in the molecule) [for example, 2,2-bis (4,4-di-t-butyl peroxide) Oxycyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate and t-butylperoxyallylcarbonate ]].
Of these, from the viewpoint of the reactivity of (A) and (b), preferred are peroxides, more preferred are monofunctional peroxides, particularly preferred are di-t-butyl peroxide, lauroyl peroxide and Dicumyl peroxide.

  The amount of (c) used is preferably 0.001 to 100%, more preferably 0, based on the weight of (b), from the reaction rate of (A) and (b), and from the viewpoint of adhesive strength and industry. 0.01 to 50%, particularly preferably 0.1 to 30%.

  Specific production methods of the acid-modified polyolefin (B) include [1] (A) and (b) heated and melted, or a suitable organic solvent [C3-18, such as hydrocarbon (for example, hexane, heptane, octane, Decane, dodecane, benzene, toluene and xylene), halogenated hydrocarbons (eg di-, tri- and tetrachloroethane and dichlorobutane), ketones (eg acetone, methyl ethyl ketone, diethyl ketone and di-t-butyl ketone) and ethers (eg Ethyl-n-propyl ether, di-i-propyl ether, di-n-butyl ether, di-t-butyl ether and dioxane)], and if necessary, a chain transfer agent (t) or a polymerization inhibitor described later. (F) and (c) [or (c Is added to a suitable organic solvent (the same as above)] and heated and stirred (melting method, suspension method and solution method), and [2] (A), (b) and if necessary ( a method (melt kneading method) in which c) and (t) are mixed in advance and melt kneaded using an extruder, a Banbury mixer, a kneader or the like.

  From the viewpoint of the reactivity between (A) and (b) and the adhesive strength, the method [1] is preferable, and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 120 to 260 ° C., more preferably from the viewpoint of the reactivity between (A) and (b) and the decomposition temperature of (B). Is 130-240 ° C.

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in a solvent, and is preferably 50 from the reactivity of (A) and (b), the decomposition temperature of (B), and an industrial viewpoint. It is -220 degreeC, More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

Examples of the chain transfer agent (t) include hydrocarbons [C6-24, such as aromatic hydrocarbons (for example, toluene, xylene, ethylbenzene and isopropylbenzene) and unsaturated aliphatic hydrocarbons (for example, 1-butene, 2-butene). 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene)] Halogenated hydrocarbons (C1-24, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, dibromomethane, tribromomethane, carbon tetrabromide, benzyl chloride and benzyl bromide); alcohols (C1-24, For example, methanol, ethanol, 1-propanol, 2-methyl-2 Propanol 1-butanol, 2-butanol and allyl alcohol); thiols (C1-24, eg ethylthiol, propylthiol, 1- and 2-butylthiol, 1- and 2-pentylthiol, 1-octylthiol and 1-dodecyl) Thiols); ketones (C3-24, such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone and ethyl butyl ketone); aldehydes (C 2-18, such as 2-methyl-2-propyl aldehyde, 1- and 2). -Butyraldehyde, 1-pentylaldehyde, 1-hexylaldehyde and 1-octylaldehyde); phenols (C6-36 such as phenol, m-cresol, p-cresol and o-cresol); quino (C6-24, eg hydroquinone); amines (C3-24, eg diethylmethylamine, triethylamine, tri-1-butylamine and diphenylamine); and disulfides (C2-24, eg diethyl disulfide, di-1-propyl disulfide, di -2-methyl-2-propyl disulfide, di-1-butyl disulfide, ethyl-1-propyl disulfide and di-1-octyl disulfide).
Of these, hydrocarbons and halogenated hydrocarbons are preferred from the viewpoint of adhesive strength, more preferred are hydrocarbons, and particularly preferred are unsaturated aliphatic hydrocarbons.
The amount of (t) used is usually 40% or less based on the weight of (A), and preferably 0 to 20% from the viewpoint of the reactivity between (A) and (b) and the adhesive strength.

Examples of the polymerization inhibitor (f) include inorganic [for example, oxygen, sulfur and metal salts (for example, ferric chloride)] and organic [catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone. (C6-24, such as p-benzoquinone and duroquinone), hydrazine (C2-36, such as 1,1-diphenyl-2-picrylhydrazine), ferrazine (C5-36, such as 1,3,5-triphenyl ferrazine) ), Nitro compounds (C3-24, such as nitrobenzene) and stable radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl-1- Piperidinyloxy (TEMPO) and 1,3,5-triphenylfeldazyl]].
The amount of (f) used is usually 5% or less based on the weight of (A), and preferably 0 to 0.5% from the viewpoint of the reactivity between (A) and (b) and the adhesive strength.

  The Mn of the modified polyolefin (B) is preferably 500 to 50,000, more preferably 1,000 to 40,000, and particularly preferably 1,500 to 30,000 from the viewpoints of adhesive strength, fluidity, and industry. is there.

  The acid value of (B) is preferably 0.5 to 300, more preferably 1 to 200, more preferably 1 to 200 from the viewpoints of adhesive strength, cohesive strength, holding power, and industry; Preferably it is 200-20,000, More preferably, it is 400-10,000. The acid value measurement method here is in accordance with JIS K 0070.

  The melting point of (B) is 40 to 120 ° C, preferably 45 to 115 ° C, more preferably 50 to 110 ° C. When the melting point is less than 40 ° C., the cohesive force and holding force decrease, and when it exceeds 120 ° C., the adhesive force decreases. Here, the melting point is a melting peak temperature obtained by a differential scanning calorimetry (DSC) method.

The hot melt adhesive of the present invention may further contain a tackifying resin (C) if necessary. (C) includes various resins, for example, bonding technology VOL. 20, (2), 13 (2000) can be used.
Examples of (C) include rosin / rosin derivative resins (Mn 200 to 1,000, such as polymerized rosin, rosin ester, phenol-modified products and unsaturated acid-modified products thereof), terpene resins [Mn 300 to 1200, such as α-pinene, β (Co) polymers such as pinene and limonene and their phenol-modified products], coumarone resin, coumarone-indene resin, petroleum resin [Mn 300 to 1,200, for example, C5 fraction, C9 fraction, C5 / C9 fraction and (Co) polymers such as dicyclopentadiene], styrene resins [Mn 500 to 5,000, for example, (co) polymers such as styrene, α-methylstyrene and vinyltoluene, having a glass transition point (hereinafter abbreviated as Tg) of 40. C. or higher], xylene resin (Mn 300 to 3,000, for example, xylene formaldehyde resin), phenol One selected from a resin (Mn 300 to 3,000, such as phenol formaldehyde resin, phenol xylene formaldehyde resin), a ketone resin (Mn 300 to 3,000, methylcyclohexanone-formaldehyde condensate) and hydrogenated products of these resins The above resin is mentioned. Among these, from the viewpoint of holding power and adhesive strength, hydrogenated terpene resin and hydrogenated petroleum resin, more preferably (co) polymerized petroleum resin of C9 fraction and C5 / C9 fraction are used. It is a hydride.

  Mn of (C) is preferably 200 to 3,000, more preferably 300 to 800 from the viewpoints of cohesive strength, holding power and fluidity, and the softening point by ring and ball type is preferably 80 to 150 ° C., more preferably 100-140 ° C.

  The hot melt adhesive of the present invention is further provided with a colorant (D1), a reinforcing agent (D2), a matting agent (D3), an antistatic agent (D4), and a dispersant as long as the effects of the present invention are not inhibited as necessary. One or more additives selected from the group consisting of (D5), flame retardant (D6), foaming agent (D7), antioxidant (D8), ultraviolet absorber (D9) and plasticizer (D10) (D) can be contained.

  Examples of the colorant (D1) include pigments such as white pigments (titanium oxide, zinc white, barium sulfate, calcium carbonate, etc.), black pigments (carbon black, iron black, aniline black, etc.), yellow pigments (yellow lead, cadmium yellow). , Iron oxide yellow, benzidine yellow, Hansa yellow, oil yellow 2G, etc.), orange pigment (red lead yellow lead, chrome vermilion, cadmium orange, pyrazolone orange, etc.), red pigment (bengala, cadmium red, permanent red, lake red C, Carmine 6B, pigment scarlet 3B, permanent red F5R, quinacridone red, thioindigo maroon, etc.), purple pigment (cobalt violet, mineral violet, etc.), blue dyed pigment (ultraviolet, bitumen, cobalt blue, phthalocyanine blue, etc.), green pigment ( lid Cyanine Green, chrome green and the like), metal powder pigments (aluminum powder, bronze powder, pearl essence etc.); dyes, such as azo, pyrazolone, stilbene, alizarin, and aniline dyes, and the like.

  As reinforcing agent (D2), metal powder (aluminum powder, copper powder, etc.), metal oxide (alumina, wollastonite, silica, clay, talc, mica, calcined kaolin, etc.), metal hydroxide (aluminum hydroxide) Etc.), metal salt (calcium carbonate, calcium silicate, etc.), fiber [inorganic fiber (carbon fiber, fiber element, α-fiber element, glass fiber, asbestos, etc.), organic fiber (cotton, jute, nylon, acrylic and rayon) Fiber etc.), microballoons (glass, shirasu, phenol resin, etc.), carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.), organic powders (wood powder, etc.), etc. Can be mentioned.

  As the matting agent (D3), inorganic, organic matting agents such as powders, granules, irregular shapes, microballoons, fibers, whiskers or fine particles, such as powders, granules or irregular shapes ( Calcium carbonate, talc, silicic acid, silicate, asbestos, mica, etc.), micro-balloon (glass, phenolic resin balloon, etc.), fibrous (glass fiber, carbon fiber, metal fiber, etc.), whisker (Ceramic whisker, titanium whisker, etc.) and fine particles (plastic fine particles, for example, polyolefin fine particles such as polyethylene and / or polypropylene).

Antistatic agents (D4) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
(1) Nonionic surfactant:
Alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, for example, active hydrogen atom-containing compounds having a hydrophobic group (C8-24 or higher) [saturated and unsaturated, higher alcohol (C8-18), higher aliphatic Amines (C8-24) and higher fatty acids (C8-24) etc .: for example alkyl or alkenyl (dodecyl, stearyl, oleyl etc.) alcohols and amines, and alkanes or alkenoic acids (eg laurin, stearin and oleic acid)] ) Oxyalkylene derivatives [AO [C2-4, such as ethylene oxide, propylene oxide, butylene oxide (hereinafter abbreviated as EO, PO, BO, respectively) and a combination of two or more of these, particularly preferably EO] (1 to 500 mol) Or more) adduct (molecular weight 17) And Mn 30,000 or less), and polyalkylene glycol [for example, polyethylene glycol (hereinafter abbreviated as PEG); higher fatty acid mono- and di-esters having a molecular weight of 150 or more and Mn 6,000 or less]; (Poly) oxyalkylene derivatives of higher fatty acid (above) esters of glycerin, pentaerythritol and sorbitan (same as above; molecular weight 320 to Mn 30,000; eg tween-type nonionics); (alkanol) amides of higher fatty acids (above) (Poly) oxyalkylene derivative (same as above; molecular weight of 330 or more and Mn of 30,000 or less); (poly) oxyalkylene derivative of polyhydric alcohol (above) alkyl (C3-60) ether (same as above; molecular weight of 180 or more and Mn 30,000) Polyoxypropylene polyol [polyhydric alcohol (above) and polyamine [C2-12, such as aliphatic, alicyclic, aromatic and heterocyclic polyamines (ethylenediamine, cyclohexanediamine, tolylenediamine, aminoethylpiperazine, etc.] )] Polyoxypropylene derivatives [eg polypropylene glycol (hereinafter abbreviated as PPG) and ethylenediamine PO adducts: Mn 500 to 5,000)] polyoxyethylene derivatives (Mn 1,000 to 30,000) [pluronic type and Tronic type nonionics]]; polyhydric alcohol (C3-60) type nonionics, such as fatty acid (above) ester of polyhydric alcohol (above), polyhydric alcohol (above) alkyl (C3-60) ether, and fatty acid ( the above ) Alkanolamides; and amine oxide type nonionics such as (hydroxy) alkyl (C10-18: dodecyl, stearyl, oleyl, 2-hydroxydodecyl, etc.) di (hydroxy) alkyl (C1-3: methyl, ethyl, 2-hydroxy) Amine oxides such as ethyl).

(2) Cationic surfactant:
Quaternary ammonium salt type cationics, for example, tetraalkylammonium salts (C11-100), such as alkyl (C8-18: lauryl, stearyl, etc.) trimethylammonium salts and dialkyl (C8-18: decyl, octyl, etc.) dimethylammonium salts Trialkylbenzylammonium salts (C17-80), such as lauryldimethylbenzylammonium salts; alkyl (C8-60) pyridinium salts, such as cetylpyridinium salts; (poly) oxyalkylenes (C2-4, degree of polymerization 1-100 or Or more) Trialkylammonium salts (C12-100), such as polyoxyethylene lauryldimethylammonium salts; and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyal Ru (C2-4) tri [(hydroxy) alkyl (C1-4)] ammonium salts, such as stearamide ethyl diethylmethylammonium salt (sapamine type quaternary ammonium salts) [these salts include, for example, halides (chlorides, bromides) Etc.), alkyl sulfates (methosulphate etc.) and salts of organic acids (below); and amine salt type cationics: 1-3 primary amines [eg higher aliphatic amines (C12-60: lauryl, stearyl and Cetylamine, cured beef tallow amine, rosinamine, etc.), polyoxyalkylene derivatives of aliphatic amines (above) (above; EO adducts, etc.), and acylaminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine ( Stearoyloxyethyl dihydroxy Ethylamine, stearamide ethyldiethylamine, etc.)] and inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) and organic acids (C2-22: acetic acid, propion, laurin, olein, succinic acid, adipine and azelaic acid, benzoic acid) Etc.) Salt.

(3) Anionic surfactant:
Carboxylic acids (salts), such as higher fatty acids (above), ether carboxylic acids [higher alcohols (above) or AO adducts thereof, such as carboxymethylated products of EO (1-10 mol) adducts], and salts thereof; sulfuric acid Ester salts such as sulfates of the above-mentioned higher alcohols or AO adducts thereof (alkyl and alkyl ether sulfates, sulfated oils (salts neutralized by sulfation of natural unsaturated fats or unsaturated waxes), sulfuric acid Sulfated fatty acid esters (salts neutralized by sulphating lower alcohol esters of unsaturated fatty acids) and sulfated olefins (salts neutralized by sulphating C12-18 olefins); sulfonates such as alkylbenzene sulfonates, Alkylnaphthalene sulfonate, sulfosuccinic acid dialkyl ester type, α-o Fin (C12-18) sulfonate and N-acyl-N-methyltaurine (eg Igepon T type); and phosphate ester salts such as higher alcohols or their AO adducts or alkyl (C4-60) phenols Phosphate salt of the AO adduct (same as above) (alkyl, alkyl ether and alkylphenyl ether phosphate).

4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics such as amino acid type amphoterics such as alkyl (C8-18) aminopropionic acid (salt), and betaine type amphoterics such as alkyl (same as above) di (hydroxy) Alkyl (above) betaine (alkyldimethylbetaine, alkyldihydroxyethylbetaine, etc.); sulfate ester (salt) type amphoterics, for example, alkyl (same as above) amine sulfate ester (salt), and hydroxyalkyl (C2-4: hydroxy) Ethyl etc.) Imidazoline sulfate ester (salt); Sulfonic acid (salt) type amphoterics, such as alkyl (same as above: pentadecyl etc.) sulfotaurine, and imidazoline sulfonic acid (salt); Foterix, for example glycerin Phosphoric acid esters of grade fatty acids (above) ester (salt).

Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.
The amine constituting the salt includes C1-20 amines such as hydroxylamine, tertiary amino group-containing diols and primary monoamines, secondary monoamines, and their alkylation (C1-4) and / or hydroxyalkylation ( C2-4) products (AO adducts): for example mono-, di- and tri- (hydroxy) alkyl (amines) (mono-, di- and tri-ethanolamine and ethylamine, diethylethanolamine, morpholine, N-methyl Morpholine, N-hydroxyethylmorpholine and the like). The quaternary ammonium salt includes a quaternized product of these amines [a quaternized product of a quaternizing agent or a dialkyl carbonate (described above) described in US Pat. No. 4,271,217].

  As the dispersant (D5), a polymer having Mn of 1,000 to 100,000, such as a vinyl resin {for example, polyolefin [for example, polyethylene, polypropylene, ethylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99], Propylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99] and ethylene / propylene / butene copolymer [copolymerization weight ratio 1 to 98/1 to 98/1 to 98], modified polyolefin [for example Oxidized polyethylene (polyethylene is oxidized with ozone, etc., and carboxyl groups, carbonyl groups and / or hydroxyl groups are introduced), polypropylene oxide (obtained in the same manner as the above oxidized polyethylene by replacing polyethylene with polypropylene), epoxy-modified polyethylene (Epoxy equivalent 100-20,000), Epoch Si-modified polypropylene (epoxy equivalent 100-20,000), hydroxyl-modified polyethylene (hydroxyl value 0.1-60), hydroxyl-modified polypropylene (hydroxyl value 0.1-60), hydroxyl-modified ethylene / butene copolymer (hydroxyl value) 0.1-60, copolymer weight ratio 1-99 / 99-1) and hydroxyl-modified propylene / butene copolymer (hydroxyl value 0.1-60, copolymer weight ratio 1-99 / 99-1)]] And vinyl resins other than the above polyolefins [eg, polyvinyl halides [eg, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride and polyiodide], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meth) acrylic acid , Poly (meth) acrylic acid esters [eg poly (meth) acrylic esters -Methyl, -ethyl, -ethyl, -n- and i-propyl and -n- and t-butyl] and styrene resins [eg polystyrene, acrylonitrile / styrene (AS) resin and acrylonitrile / butadiene / styrene (ABS) resin] };

  Polyester resins [eg polyalkylene (C2-24) terephthalate [eg polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)], polyalkylene (C2-24) isophthalate [eg polyethylene isophthalate and polybutylene isophthalate] and poly -P-phenylene esters [eg poly-p-phenylene malonate, poly-p-phenylene adipate and poly-p-phenylene terephthalate]]; polyamides [eg polycoupleramide (6-nylon), polyhexamethylene adipamide (6, 6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon), poly-ω-aminoheptanoic acid (7-nylon) and poly-ω- Aminononanoic acid (9-nylon)]; polyether resins [eg polyoxymethylene, polyoxyethylene, polyoxyphenylene and poly-1,3-dioxolane]; polycarbonate resins; polyphenylene resins (PPO); Examples include coalescence.

  As flame retardant (D6), organic flame retardant [phosphorus-containing compound [phosphate ester (tricresyl phosphate etc.) etc.], bromine containing compound (tetrabromobisphenol A, decabromobiphenyl ether etc.), chlorine containing Compounds (such as chlorinated paraffin and anhydrous heptic acid)], inorganic flame retardants [antimony trioxide, magnesium hydroxide, borate, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, magnesium hydroxide, polyphosphorus] Acid ammonium, etc.].

  As the foaming agent (D7), gaseous foaming agents [carbon dioxide (carbon dioxide), nitrogen, oxygen, argon, chlorofluorocarbon, etc.]; volatile liquid foaming agents [hydrocarbons (C4-8, such as pentane, neopentane, butane) Hexane, heptane), chlorinated hydrocarbons (C1-4, such as methyl chloride, methylene chloride, trichloroethylene, dichloroethane), fluorinated hydrocarbons (C1-3, such as CFC-11, CFC-12, CFC-113, CFC) -141b), water, alcohol, benzene, toluene, xylene, mesitylene, etc.]; thermal decomposition solid foaming agent [azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, toluenesulfonylhydrazide, 4,4-oxybis ( Benzenesulfonyl hydrazide) and the like]. These foaming agents may be used alone or in combination of two or more.

  Antioxidants (D8) include hindered phenols [pt-amylphenol / formaldehyde resin, 2,6-bis (1-methylheptadecyl) -p-cresol, butylated cresol, styrenated cresol, 4 , 4'-butylidenebis (6-tert-butyl-m-cresol), 4,4'-cyclohexylidenebis (2-cyclohexylphenol), 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, octadecyl -3,5-di-t-butyl-4-hydroxycinnamate, butylated hydroxyanisole, propyl gallate, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid (NDGA), 2,6-di -T-butyl-4-methylphenol (BHT), 2-t-butyl-4-methyl Enol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B), 2-t-butyl-4-ethylphenol, 2,6- Di-t-butyl-4-ethylphenol, n-octadecyl-3- (4′-hydroxy-3,5-di-t-butylphenyl) propionate, 4,4′-butylidenebis (6-t-butyl-3) -Methylphenol), 4,4'-methylenebis (6-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6- t-butylphenol), 2,2′-thiobis (6-t-butyl-4-hydroxy-2-methylphenol), 1,6-bis (3,5-di-t-butyl-4-hydroxy-2-me Ruphenyl) butane, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy) Benzyl) mesitylene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxymethyl] methane etc.];

Sulfur-containing system [N, N′-diphenylthiourea, dimyristylthiodipropionate, dilaurylthiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), distearylthiodipropionate , 6- (4-oxy-3,5-di-t-butylanilino) 2,4-bis (n-octylthio) -1,3,5-triazine, 4,4′-thiobis (6-t-butyl- 3-methylphenol), 4,4′-thiobis (6-t-butyl-o-cresol) and the like];

Phosphorus-containing [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, phosphite ester resin, tris (nonylphenyl) phosphite, Dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate etc.] and the like.

Examples of the ultraviolet absorber (D9) include salicylates (phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.);
Benzophenone [2,4-dihydroxyzenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy -4-methoxy-5-sulfobenzophenone (trihydrate), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 4 -Dodecyloxy-2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone and the like]; and benzotriazole series [2- (2′-hydroxy-5′-methylphenyl) -benzotriazole and the like] and the like.

  Examples of the plasticizer (D10) include adhesion technology VOL. 20, (2), 21 (2000), for example, process oil (Mn 300 to 10,000, for example, paraffin, naphthene and aromatic ring-containing process oil), resin exhibiting a liquid state at room temperature (20 to 25 ° C.) Mn 300 to 10,000, such as liquid polybutene, liquid polybutadiene, and liquid polyisoprene), hydrogenated resin hydride, natural or synthetic wax [Mn 300 to 30,000, such as paraffin wax, microcrystalline wax, low molecular weight polyolefin Wax (Mn 1,000 to 30,000)], and a mixture of two or more thereof.

The total amount of (D) in the adhesive of the present invention is usually 30% or less based on the total weight of the adhesive, and preferably 1 to 10% from the functional expression of (D) and an industrial viewpoint. .
The amount of each additive (D) used based on the total weight of the adhesive is as follows: (D1) is usually 10% or less, preferably 1 to 5%; (D2) is usually 15% or less, preferably 3 to 10%. (D3) is usually 20% or less, preferably 1 to 10%; (D4) is usually 10% or less, preferably 1 to 5%; (D5) is usually 20% or less, preferably 0 to 15%, especially Preferably 0 to 10%; (D6) is usually 15% or less, preferably 3 to 10%; (D7) is usually 1 to 20% or less, preferably 5 to 15%; (D8) is usually 3% or less, Preferably it is 0.01 to 1%; (D9) is usually 3% or less, preferably 0.01 to 1%; (D10) is usually 20% or less, preferably 5 to 15%.
When the additive is the same and overlaps between (D1) to (D10), the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive. Considering that the effect as an additive can be obtained at the same time, the amount used is adjusted according to the purpose of use.

Although it does not specifically limit as a hot-melt-adhesive manufacturing method of this invention, For example, (1) (A), (B) and (C) and (D) which are added as needed are heat-melted (normally 80-250 degreeC) mixing. (2) A method in which an organic solvent (toluene, xylene, etc.) is added and each component is dissolved by heating (usually 60 to 180 ° C.), mixed uniformly, and then the solvent is distilled off. In any method, it is preferable to carry out in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration. Among the above methods, the method (1) is preferable from the industrial viewpoint.
Moreover, a heating melt kneader can be used as the mixing device. The heating melt kneader is not particularly limited in its form, shape, etc. For example, a mixer having a highly compressible screw or ribbon stirrer, a kneader, a single-screw or multi-screw extruder, a mixer Etc.

  Examples of the method for applying the hot melt adhesive of the present invention to an adherend include, but are not limited to, methods such as spiral coating, bead coating, roll coating, and slot coating. Moreover, the melting temperature when applied to the adherend is usually 100 to 200 ° C., the melt viscosity is usually 1 to 500 Pa · s, and preferably 2 to 100 Pa · s from the viewpoint of coating properties.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight”, “retention ratio in impact strength” and “%” other than mol% represent “% by weight”.
Production Example 1
Propylene / 1-butene copolymer high molecular weight polyolefin (Mn 100,000) heat-degraded (performed under normal pressure, 360 ° C. × 80 minutes under nitrogen gas flow), 75 mol% of propylene , 80 parts of a low molecular weight polyolefin with Mn 4,500 and 3.1 carbon double bonds per 1,000 carbons, containing 25 mol% of 1-butene as a structural unit, is placed in a three-necked flask with a cooling tube and purged with nitrogen Then, the mixture was heated to 180 ° C. and melted under a nitrogen stream.
To this, 10 parts of maleic anhydride was added and mixed uniformly, then 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene was added dropwise, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified polyolefin (B1) having a melting point of 82 ° C. and Mn of 5,000.

Production Example 2
In Production Example 1, the low molecular weight polyolefin obtained by thermal degradation is composed of 80 mol% of propylene and 20 mol% of 1-butene, Mn is 4,500, and the number of double bonds per 1,000 carbon atoms. The acid-modified polyolefin (B2) having a melting point of 90 ° C. and a Mn of 5,000 was obtained in the same manner as in Production Example 1 except that the number of Mn was 5,000.

Production Example 3
In Production Example 1, the low molecular weight polyolefin obtained by thermal degradation is composed of 85 mol% propylene and 15 mol% 1-butene as structural units, Mn is 4,500, and the number of double bonds per 1,000 carbon atoms. Was performed in the same manner as in Production Example 1 except that 3.1 was 3.1 to obtain an acid-modified polyolefin (B3) having a melting point of 110 ° C. and a Mn of 5,000.

Comparative production example 1
In Production Example 1, the low molecular weight polyolefin obtained by thermal degradation is 70 mol% of propylene obtained by thermal degradation of a high molecular weight polyolefin (Mn 80,000) which is a propylene / ethylene / 1-butene copolymer. In the same manner as in Production Example 1, except that 5 mol% of ethylene and 25 mol% of 1-butene are structural units, Mn is 4,500, and the amount of double bonds per 1,000 carbon atoms is 3.1. The modified polyolefin (B4) having a melting point of 80 ° C. and Mn of 5,000 was obtained.

Comparative production example 2
In Production Example 1, the low molecular weight polyolefin obtained by thermal degradation is 98 mol% of propylene and 2 mol of ethylene obtained by thermal degradation of a high molecular weight polyolefin (Mn 70,000) which is a propylene / ethylene copolymer. % As a structural unit, Mn is 4,500, and the number of double bonds per 1,000 carbons is 3.0. A modified polyolefin (B5) was obtained.

Examples 1-3 and Comparative Examples 1-2
Heated melt kneader ["KRC S1", capable of continuous mixing, with a jacket heating medium temperature set to 160 ° C, a diameter D of 1 inch, and a screw shaft length L of 10 inches (L / D ratio = 10). Kurimoto Tekko Co., Ltd.], 80 parts each of (B1) to (B5) and tackifying resin [partially hydrogenated petroleum resin (C9 fraction copolymer main component) “Arcon M-115”, Arakawa Chemical ( Co., Ltd.] 20 parts of each were blended and melt-kneaded to obtain hot melt adhesives (H1) to (H5).

Comparative Example 3
In Example 1, instead of 80 parts of (B1), 80 parts of styrene-ethylene-propylene-styrene block copolymer rubber [trade name “KL-2003”, manufactured by Kuraray Co., Ltd.] (hereinafter abbreviated as SEPS) was used. Except for this, the same procedure as in Example 1 was carried out to obtain a hot melt adhesive (H6).

Performance test example About each hot-melt-adhesive obtained in Examples 1-3 and Comparative Examples 1-3, T-type peeling adhesive strength, holding power, and fluidity | liquidity were evaluated with the following test method. The results are shown in Table 1. The cohesive force can be evaluated by holding force, and was included in the following performance evaluation item (2) holding force.

(1) T-type peel adhesive strength Each hot melt adhesive is applied to one side of a polypropylene nonwoven fabric having a length of 150 mm, a width of 25 mm and a thickness of 0.5 mm (adhesive temperature of 120 ° C., coating amount of 0.04 g / m ² ), and a polypropylene nonwoven fabric or PET film having the same shape was stacked and bonded at 100 ° C. under a load of 500 g / m ² . Then, after standing at 25 ° C. for 24 hours, in accordance with JIS K 6854-3, the peel strength is measured at a tensile rate of 300 mm / min using an autograph, and the maximum peel strength is determined as a T-type peel. The adhesive strength was used (unit: g / 25 mm).
(2) Holding force A hot melt adhesive is applied to a steel plate having a length of 125 mm, a width of 50 mm, and a thickness of 1.5 mm at a thickness of 40 μm (applied to the area of a PET film to be bonded, which will be described later), and the length is formed thereon. A PET film of 100 mm × width 25 mm × thickness 1.5 mm was bonded using a roller in accordance with JIS Z 0237. In accordance with JIS Z 0237, a 100 g weight was suspended from the test piece in an atmosphere of 50 ° C., and the distance from the peeling start position to the peeling position after 60 minutes was measured to obtain a holding force (unit: mm). .
(3) Fluidity A test piece was prepared by cutting a hot melt adhesive (solid) into a length of 10 mm, a width of 10 mm, and a thickness of 5 mm with an ultrasonic cutter. A double-sided tape was attached to a polypropylene plate having an inclination angle of 45 °, and was allowed to stand in an atmosphere at a temperature of 120 ° C. for 5 minutes.

（注）ＰＥＴ：ＰＥＴフィルム
ＮＷ ：ポリプロピレン不織布

(Note) PET: PET film NW: Polypropylene nonwoven fabric

  The hot melt adhesive of the present invention is excellent in fluidity, cohesive strength, holding power and adhesive strength, and therefore has a wide range of adherends (for example, various plastic molded articles, rubber, paper, cloth, metal, wood, glass, mortar). It can be applied to concrete), but is particularly difficult to adhere to polyolefin (polyethylene, polypropylene, etc.) resin molded articles (for example, an adhesive between a polyolefin nonwoven fabric and a polyolefin film constituting a disposable diaper), or these and the above It can be suitably used as a hot melt adhesive for bonding to other adherends and is extremely useful.

Claims (5)

C-C12 alpha olefin (a) 15-70 mol%, 30-85 mol% of propylene, and polyolefin (A) which makes ethylene 0-1 mol% a structural unit are acid-modified, 50-120 A hot melt adhesive comprising an acid-modified polyolefin (B) having a melting point of ° C. The adhesive according to claim 1, wherein (A) has 0.2 to 10 double bonds per 1,000 carbon atoms at the molecular end and / or in the molecule. The adhesive according to claim 1 or 2, wherein (A) is a polyolefin having a number average molecular weight of 500 to 40,000 obtained by thermally degrading a high molecular weight polyolefin (A0). The adhesive according to any one of claims 1 to 3, further comprising a tackifying resin. Further, one or more other selected from the group consisting of a colorant, a reinforcing agent, a matting agent, an antistatic agent, a dispersant, a flame retardant, a foaming agent, an antioxidant, an ultraviolet absorber and a plasticizer. The adhesive according to any one of claims 1 to 4, further comprising an additive.