JP2017105992A - Hot-melt adhesive composition and bonded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot-melt adhesive composition excellent in wettability to hydrophilic substrates and excellent in adhesive strength to hydrophilic substrates.SOLUTION: A hot-melt adhesive composition (E) contains: a polyurethane (A) which is a reaction product of a polyisocyanate (a) and a polyol (b) containing an aromatic diol (b1) and an aliphatic polyether polyol (b2); and an aliphatic polyether polyol (B). The hot-melt adhesive composition (E) contains 45-70 wt.% of oxyethylene groups based on the weight of the hot-melt adhesive composition (E). The composition preferably has a melt viscosity at 150°C of 0.1-10 Pa s.SELECTED DRAWING: None

Description

The present invention relates to a hot-melt adhesive composition, and more particularly to a hydrophilic hot-melt adhesive composition having excellent adhesive strength with a hydrophilic substrate.

Hot-melt adhesives do not contain solvents and can be used simply by heating and can be bonded at high speed. Is used.

Among them, a carboxyl group-containing polyurethane resin having a hydroxyl group at the terminal obtained by reacting a specific polyol and polyisocyanate as a hot melt adhesive having excellent adhesion strength and water resistance to hydrophilic substrates such as cloth and paper There is known a polyurethane hot melt adhesive (see Patent Document 1).

JP 2007-182515 A

However, the hot melt adhesive described in Patent Document 1 has a problem that the wettability with respect to the hydrophilic substrate is not sufficient and the adhesive strength with respect to the hydrophilic substrate is not sufficient.
The objective of this invention is providing the hot-melt-adhesive composition excellent in the wettability with respect to a hydrophilic base material, and excellent in the adhesive strength with a hydrophilic base material.

As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention is a hot melt adhesive composition comprising a polyurethane (A) and an aliphatic polyether polyol (B), wherein (A) is a polyisocyanate (a) and an aromatic diol (b1). And a polyol (b) containing an aliphatic polyether polyol (b2), and the hot melt adhesive composition contains 45 to 70% by weight of oxyethylene groups based on the weight of the composition Adhesive composition (E); and an adhesive body having an adhesive layer comprising the hot-melt adhesive composition (E).

The hot melt adhesive composition of the present invention is excellent in wettability with respect to a hydrophilic substrate and excellent in adhesive strength with the hydrophilic substrate. Therefore, it is extremely useful as an adhesive for forming an adhesive body with a hydrophilic substrate such as cloth and paper.

The hot melt adhesive of the present invention comprises a polyurethane (A) which is a reaction product of a polyisocyanate (a) and a polyol (b) containing an aromatic diol (b1) and an aliphatic polyether polyol (b2) and an aliphatic. A hot melt adhesive composition (E) containing a polyether polyol (B), and containing 45 to 70% by weight of oxyethylene groups with respect to the weight of the hot melt adhesive composition (E).

The polyisocyanate (a) is at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanate (a1), alicyclic polyisocyanate (a2), araliphatic polyisocyanate (a3) and aromatic polyisocyanate (a4). Isocyanate. Preferred examples of the aliphatic polyisocyanate (a1) include aliphatic polyisocyanates having 2 to 18 carbon atoms, such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also referred to as HDI), dodecamethylene diisocyanate, 1,6. , 11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) Examples thereof include carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

Preferred examples of the alicyclic polyisocyanate (a2) include alicyclic polyisocyanates having 4 to 15 carbon atoms, such as isophorone diisocyanate (also referred to as IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI). Also cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (also referred to as hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6- Examples include norbornane diisocyanate.

Preferred examples of the araliphatic polyisocyanate (a3) include araliphatic polyisocyanates having 8 to 15 carbon atoms, including m- or p-xylylene diisocyanate (also referred to as XDI) and α, α, α ′, and α′-tetramethylxylylene diisocyanate (also referred to as TMXDI).

Preferred examples of the aromatic polyisocyanate (a4) include aromatic polyisocyanates having 6 to 20 carbon atoms, such as 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene. Isocyanate (also referred to as TDI), crude TDI, 2,4′- or 4,4′-diphenylmethane diisocyanate (also referred to as MDI), crude MDI, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4 , 4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and m- Or p-isocyanatophenyl sulfonyl isocyanate etc. are mentioned.

Among these, HDI, IPDI, TDI, MDI, XDI and TMXDI are preferable from the viewpoint of easy availability, and HDI, MDI and XDI are particularly preferable. These polyisocyanates (a) may be used individually by 1 type, and may use 2 or more types together.

The polyol (b) includes an aromatic diol (b1) and an aliphatic polyether polyol (b2).
As the aromatic diol (b1), any diol having two hydroxyl groups and an aromatic ring structure can be used without limitation, and a bifunctional phenol (b11) having 6 to 27 carbon atoms and alkylene oxide thereof (hereinafter, And adduct (b12) (abbreviated as AO).
Examples of the bifunctional phenol (b11) having 6 to 27 carbon atoms include monocyclic diphenols, condensed polycyclic diphenols, and bisphenols.
Examples of monocyclic diphenols include resorcinol, catechol and hydroquinone.
Examples of the condensed polycyclic diphenol include 1,5-dihydroxynaphthalene and 1,4-dihydroxynaphthalene.
Bisphenols include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E. Bisphenol F, bisphenol G, bisphenol P, bisphenol Z, bisphenol S and the like.
Among them, bisphenols are preferable from the viewpoint of adhesive strength and the like, and 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bisphenol A, bisphenol E, bisphenol F and bisphenol S are preferable. Further preferred.

When the aromatic diol (b1) is an AO adduct of a bifunctional phenol having 6 to 27 carbon atoms, examples of AO include AO having 2 to 4 carbon atoms, and examples of AO having 2 to 4 carbon atoms include 1, 2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, ethylene oxide (hereinafter abbreviated as EO), 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide And mixtures thereof.
As AO, EO, PO and a mixture thereof are particularly preferable, and EO is more preferable.
The AO added to the aromatic diol having 6 to 27 carbon atoms may be one of the above AOs or may be used in combination of two or more.
When two or more kinds of AO are used in combination, the binding format may be added in block format (chip type, balance type, active secondary type, etc.), may be added in random format, block format and random The formats may be mixed. Especially, it is preferable to add in block form from viewpoints of adhesive strength or the like.
As for whether the addition format when two or more alkylene oxides are used in combination is a random format or a block format, various NMR analyzes (1H, 13C, DEPT, HMQC) and mass spectrometry applying Whithout-NOE measurement are used. (Ionization method: ESI-MS) can be analyzed.

The number of moles of AO added to the bifunctional phenol having 6 to 27 carbon atoms is preferably 2 to 100 moles, more preferably 2 to 30 moles per mole of the bifunctional phenol.
Addition of AO to an aromatic diol having 6 to 27 carbon atoms is a known method in which alkylene oxide is added dropwise simultaneously or sequentially under reduced pressure at 100 to 200 ° C. in the presence of an alkali catalyst such as potassium hydroxide. Can be done.

As the aromatic diol (b1), an aromatic diol (b11) represented by the following general formula (1) is preferable.

In the formula, -Y- is a direct bond or a methylene group, a dimethylmethylene group, a methylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, and among them, a dimethylmethylene group is preferable. Z represents an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include a propylene group, an ethylene group, a butylene group, a methylethylene group, a 1-methylbutylene group, and 1,1′-dimethylethylene. Group, 2-methylpropylene group, ethylethylene group and the like, among which ethylene group and methylethylene group are preferable, and ethylene group is more preferable.
m and n are integers of 1 or more, and m + n is 2 to 100 (preferably 2 to 30).

The aromatic diol (b11) represented by the general formula (1) is 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) sulfide, bisphenol A, bisphenol E, bisphenol F. Alternatively, it can be obtained by adding PO and / or EO to bisphenol S by the method described above.

Examples of the aliphatic polyether polyol (b2) include an aliphatic dihydric alcohol having 2 to 8 carbon atoms, an alicyclic group-containing dihydric alcohol having 6 to 10 carbon atoms, an aliphatic trihydric alcohol, and an aliphatic tetrahydric or higher alcohol. And AO adducts of at least one aliphatic alcohol selected from the group consisting of and AO adducts of compounds having a primary or secondary amino group.

Examples of the aliphatic dihydric alcohol having 2 to 8 carbon atoms include linear diols having 2 to 8 carbon atoms (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, etc.) and diols having a branched alkylene chain having 2 to 8 carbon atoms (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl- 1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol) and the like.

Examples of the alicyclic group-containing dihydric alcohol having 6 to 10 carbon atoms include 1,4-bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane.

Examples of the aliphatic trihydric alcohol include aliphatic trihydric alcohols having 2 to 6 carbon atoms (such as glycerin, trimethylolpropane and trialkanolamine), and examples of the aliphatic tetravalent or higher alcohols include those having 5 to 5 carbon atoms. 10 aliphatic 4- to 6-valent alcohols (pentaerythritol, diglycerin, triglycerin, dipentaerythritol, sorbit, sorbitan, sorbide, etc.).

Examples of the compound having a primary or secondary amino group include alkyl (C1-12) amine (monomethylamine, monoethylamine, monobutylamine, dimethylamine, diethylamine, dibutylamine, etc.) and poly (n = 2 to 6). Alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, etc.) It is done.

The above-mentioned compounds having an aliphatic alcohol and a primary or secondary amino group may be used alone or in combination of two or more.
Among these, aliphatic alcohols are preferable, aliphatic dihydric alcohols having 2 to 8 carbon atoms are more preferable, and ethylene glycol or 1,2-propanediol is particularly preferable.

When the aliphatic polyether polyol (b2) is an AO adduct, examples of the AO to be added include the same AO as exemplified for the aromatic diol (b1), and EO, PO, and a mixture thereof are preferable.
In the case where the aliphatic polyether polyol (b2) has two or more kinds of AO added thereto, the bonding form may be added in block form (chip type, balance type, active secondary type, etc.), and random form. The block format and the random format may be mixed.

The AO added to the aliphatic polyether polyol (b2) is preferably added in an amount of 3 to 500 mol with respect to 1 mol of the compound having the aliphatic alcohol and the primary or secondary amino group.

When the aliphatic polyether polyol (b2) is obtained by adding EO and PO in a block form or a random form to the aliphatic alcohol and the compound having a primary or secondary amino group, the AO is It is preferable that 1 to 400 moles of EO and PO are added to 1 mole of the compound having an aliphatic alcohol and a primary or secondary amino group, EO is added to 20 to 350 moles, and PO is 10 to 10 moles. It is more preferable that 250 is added, and it is particularly preferable that EO and PO are added at a weight ratio (EO / PO) of 90/10 to 10/90.

The aliphatic polyether polyol (b2) is preferably an AO adduct of an aliphatic dihydric alcohol having 2 to 8 carbon atoms, and further an EO and / or PO adduct of an aliphatic dihydric alcohol having 2 to 8 carbon atoms. Preferred are EO and / or PO adducts of ethylene glycol and EO and / or PO adducts of 1,2-propanediol.
The EO adduct of ethylene glycol is commercially available as polyethylene glycol, the PO adduct of ethylene glycol and the PO adduct of 1,2-propanediol as polypropylene glycol.

When the aliphatic polyether polyol (b2) is an AO adduct of the above aliphatic alcohol and an AO adduct of a compound having a primary or secondary amino group, the above aliphatic alcohol and primary or secondary amino group It can obtain by adding AO to the compound which has this by the same method as the method illustrated by aromatic diol (b1).

The aliphatic polyether polyol (b2) preferably has a number average molecular weight (hereinafter abbreviated as Mn) of 200 to 20,000, more preferably 600 to 10,000.
The number average molecular weight of the aliphatic polyether polyol (b2) can be measured, for example, under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel”
Super H2000, TSKgel SuperH3000, and TSKgel SuperH4000 connected to each one "[all manufactured by Tosoh Corporation]
・ Sample solution: 0.25 wt% tetrahydrofuran solution ・ Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

The polyol (b) may contain other polyols other than the aromatic diol (b1) and the aliphatic polyether polyol (b2). Examples of the other polyol (b3) include polyester polyol, silicone polyol, polymer polyol, Examples include diene polyols (polybutadiene polyols, etc.), hydrogenated products of polydiene polyols, acrylic polyols, natural oil polyols (castor oil, etc.), and modified natural oil polyols.

The content of the aromatic diol (b1) and the aliphatic polyether polyol (b2) contained in the polyol (b) is 1 to 50% by weight of the aromatic diol (b1) based on the total weight of the polyol (b). (Further preferably, it is 5 to 35% by weight), and the aliphatic polyether polyol (b2) is preferably 50 to 99% by weight (more preferably 65 to 95% by weight).

The weight ratio [(b1) / (b2)] of the aromatic diol (b1) and the aliphatic polyether polyol (b2) is preferably 1/99 to 50/50.

The polyurethane (A) is produced by polymerization by a known method such as a method of mixing and heating the polyisocyanate (a), the aromatic diol (b1) and the aliphatic polyether polyol (b2). For example, (i) the total number of moles of active hydrogen groups in the aromatic diol (b1) and the aliphatic polyether polyol (b2) is greater than the number of moles of isocyanate groups in the polyisocyanate (a). A method of obtaining polyurethane (A) by reacting in excess, and (ii) the number of moles of isocyanate group of polyisocyanate (a) is changed to the aromatic diol (b1) and the aliphatic polyether polyol (b2). After obtaining an isocyanate group-terminated urethane prepolymer by reacting in excess of the total number of moles of active hydrogen groups The aromatic diol (b1) and / or the aliphatic polyether polyol (b2) in an amount that makes the amount of active hydrogen groups (number of moles) larger than the number of moles of isocyanate groups of the isocyanate group-terminated urethane prepolymer, and further The method of making it react and obtaining a polyurethane (A) etc. are mentioned.
Of these, the method (ii) is preferable from the viewpoint of simplicity of the production process.

In producing the polyurethane (A), a known urethanization catalyst used in the production of a conventional polyurethane may be used, and a metal catalyst [tin catalyst (trimethyltin laurate, trimethyltin hydroxide, Dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.), lead-based catalysts (lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.) and others Metal catalysts (metal naphthenates such as cobalt naphthenate, phenylmercuric propionates, etc.)] and amine catalysts {triethylenediamine, tetramethylethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4, 0] -7-Undecene (Brand name: DBU, Sun Apro Manufactured, registered trademark, etc.), dialkylaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, etc.), heterocyclic aminoalkylamines [2- (1-aziridinyl) Ethylamine and 4- (1-piperidinyl) -2-hexylamine etc.] carbonates and organic acid salts (formate etc.), N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine, etc. }, And two or more of these may be used in combination.

The weight average molecular weight (hereinafter abbreviated as Mw) of the polyurethane (A) contained in the hot melt adhesive composition of the present invention is preferably 10,000 to 150,000, more preferably 15,000 to 100,000. . When it is in this range, the resin strength of the adhesive and the coating property to the substrate are improved, which is preferable.

In addition, Mw of a polyurethane (A) can be measured on condition of the following using GPC.
・ Device: HLC-8220GPC [manufactured by Tosoh Corporation]
Column: “Guardcolumn α”, “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125% by weight N, N-dimethylformamide solution Solution injection amount: 10 μL
・ Flow rate: 0.6 mL / min Reference material: Standard polystyrene column temperature: 40 ° C.

The isocyanate group content of the polyurethane (A) is a mass fraction of the amount of isocyanate groups remaining in the polyurethane (A), and is preferably 0.02% or less based on the weight of the polyurethane (A). More preferably, it is 0.01% or less. When the isocyanate group content is in this range, the coating property to the substrate is good, which is preferable.
In addition, the isocyanate group content rate of a polyurethane (A) can be measured by A method as described in JISK1603-1: 2007 Plastics-Polyurethane raw material aromatic isocyanate test method-Part 1: Determination of isocyanate group content rate. .

Examples of the aliphatic polyether polyol (B) contained in the hot melt adhesive composition of the present invention include the same aliphatic polyether polyol (b2), and (B) and (b2) are the same. It may or may not be. The preferable thing of (B) is the same as the preferable thing of (b2).
The case where the aliphatic polyether polyol (B) is the same polyol as the aliphatic polyether polyol (b2) constituting the polyurethane (A) is particularly preferable.

The weight ratio of the polyurethane (A) and the aliphatic polyether polyol (B) contained in the hot melt adhesive composition of the present invention is preferably 90/10 to 10/90, more preferably from the viewpoint of adhesive strength and the like. Is 85/15 to 15/85, more preferably 80/20 to 20/80, and particularly preferably 80/20 to 40/60.

The hot melt adhesive composition (E) of the present invention has a melt viscosity at 150 ° C. of preferably 0.1 to 10 Pa · s, more preferably 0.5 to 8 Pa · s from the viewpoint of coating properties and the like. More preferably, it is 2 to 7 Pa · s.
The melt viscosity at 150 ° C. of the hot melt adhesive composition can be adjusted by the composition of the polyurethane (A) and Mw and the ratio of the polyurethane (A) and the aliphatic polyether polyol (B), and these are preferred ranges. By making it into, the melt viscosity in 150 degreeC can be made into a preferable range.

The melt viscosity at 150 ° C. can be measured using a rotary viscometer (RB viscometer and No. 4 rotor, manufactured by Toki Sangyo Co., Ltd.) based on JIS K7117-1: 1999.

The hot melt adhesive composition (E) contains 45 to 70% by weight of oxyethylene groups with respect to the weight of the hot melt adhesive composition (E), and is preferably from the viewpoint of wettability to a hydrophilic substrate. It contains 47 to 65% by weight, more preferably 50 to 60% by weight.
When the oxyethylene group content is less than 45% by weight, the wettability to the hydrophilic substrate is insufficient, and when the oxyethylene group content exceeds 70% by weight, the peel strength is insufficient.

In the hot melt adhesive composition of the present invention, the contact angle of water with respect to the hot melt adhesive composition measured by a droplet method is preferably 0 to 60 degrees from the viewpoint of wettability to a hydrophilic substrate and the like. -60 degrees is more preferable. A low water contact angle with the hot melt adhesive composition means that the hot melt adhesive composition has a high hydrophilicity. The higher the hydrophilicity of the hot melt adhesive composition, the wettability with respect to the hydrophilic substrate. Becomes better. In addition, the contact angle of water with respect to the hot melt adhesive composition is the ratio of the aromatic diol (b1) to the aliphatic polyether polyol (b2) in the polyurethane (A) contained in the hot melt adhesive composition and the polyurethane ( The ratio between A) and the aliphatic polyether polyol (B) can be adjusted within a preferable range, and the contact angle can be set within a preferable range by setting these to a preferable range.

In addition, the contact angle of water by the droplet method can be measured by the following measuring method.
(Measurement method of contact angle)
A hot melt adhesive composition is heated to 130 ° C., applied to a PET film with a thickness of 1.0 mm, and cooled to room temperature to prepare a contact angle measurement sample.
Subsequently, the contact angle (25 degreeC, 0.5 second after) of the said contact angle measurement sample and water is measured using a fully automatic contact angle meter [Kyowa Interface Science Co., Ltd. product, PD-W].

The hot melt adhesive composition of the present invention preferably further contains an antioxidant and / or a weather resistance stabilizer.

Antioxidants 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 phenols [1,3, 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di t-butyl-4-hydroxyphenyl) propionate, etc.]; 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, diphenylisodecyl 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-t-butylphenylditridecyl) phosphite, cyclic neopentane Tetrayl 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, and the like phenothiazines like].
These antioxidants are commercially available as the Irganox series (Irganox is a registered trademark of BASF Societas Europe).

Examples of the weather resistance stabilizer include known ultraviolet absorbers [benzotriazole (2- (2′-hydroxy-5′-methylphenyl) benzotriazole, etc.), triazine (bisresorcinyl triazine, bisethylhexyloxyphenol methoxy). Phenyltriazine and octyltriazone), benzophenone series (2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone etc.), benzoate series (2,4-di-tert-butylphenyl-3,5-di-) tert-butyl-4-hydroxybenzoate etc.)], known light stabilizers [hindered amines etc. (bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.)], etc. But benzotriazole, triazine and benzophenone It is preferred.
The weather resistance stabilizer is commercially available as the TINUVIN series (TINUVIN is a registered trademark of BASF Societas Europe).

When the hot melt adhesive composition of the present invention contains an antioxidant and a weathering stabilizer, the content of the antioxidant and the weathering stabilizer is 0.1 from the viewpoint of oxidation resistance and weatherability, respectively. It is preferable that it is 10 to 10 weight%, More preferably, it is 0.2 to 5 weight%, respectively.

The hot melt adhesive composition of the present invention comprises a method of melt-mixing polyurethane (A) and polyether polyol (B) and antioxidants and weathering stabilizers used as necessary, organic solvents (toluene, xylene and acetic acid). In the presence of ethyl, etc., the polyurethane (A) and the polyether polyol (B), and the antioxidant and weathering stabilizer used as necessary are heated and dissolved, mixed uniformly, and then the solvent is distilled off. Can be obtained.
Examples of the mixing apparatus include known heat-melt kneaders (pressure reactor with a stirrer, mixer having a screw or ribbon stirrer, kneader, uniaxial or multi-screw extruder, mixer, and the like).
The mixing temperature is preferably 100 to 250 ° C., and is preferably performed in an inert gas atmosphere such as nitrogen gas in order to prevent resin deterioration.

The adhesive body of this invention is an adhesive body which has the contact bonding layer which consists of said hot-melt-adhesive composition. The adhesive layer is coated with (Method 1) a method of melt-coating the hot-melt adhesive composition on at least one of the adherends, and (Method 2) a hot-melt adhesive formed into a film or the like. It can form by the method etc. which arrange | position between adhesive bodies.
As the method of coating in (Method 1), known coating methods such as spiral coating, spray coating, roll coating, slot coating, control seam coating and bead coating can be used. The melting temperature is preferably 100 to 250 ° C.

Examples of the adherend include various plastic molded articles, rubber, paper (tissue etc.), cloth (cotton, silk etc.), metal, wood, glass and mortar concrete. It can be preferably applied.
When the adhesive layer of the present invention is formed by the above (Method 1), it can be obtained by adhering the other adherend to the adhesive layer immediately after melt coating. ), The film-like adhesive layer disposed between the adherends can be heated and melted.

The adhesive body of the present invention is not particularly limited as long as it is an adhesive body having an adhesive layer made of the hot melt adhesive composition described above, but an adhesive body comprising a hydrophilic substrate such as paper and cloth [rain gear, Water-based products (such as bath mats), water treatment equipment (such as filters), and sanitary materials (such as disposable disposable diapers and sanitary products) are preferred.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.

<Production Example 1>
An autoclave was charged with 35 parts of 1,2-propanediol and 3 parts of a 50% aqueous solution of potassium hydroxide (manufactured by Toagosei Co., Ltd.). . Next, 320 parts of PO and 1410 parts of EO were simultaneously injected at 105 to 130 ° C. in about 3 hours, and the reaction was continued at the same temperature until the volatile content became 0.1% or less, and further vacuum dehydration at 120 ° C. for 60 minutes. The water content was 0.05 wt% or less. Water and an alkali adsorbent (KYOWARD 600, manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the obtained reaction product, filtered, and then subjected to heat dehydration to obtain an aliphatic polyether polyol (b2-1).
Mn of the obtained aliphatic polyether polyol (b2-1) is 4000, and the added moles of EO and PO with respect to 1 mole of 1,2-propanediol are 72 moles of EO and 13 moles of PO, respectively. The binding mode of EO and PO was random, and the ratio of EO based on the total weight of EO and PO was 80% by weight.
In a reaction vessel equipped with a stirrer, 100 parts of the above-mentioned aliphatic polyether polyol (b2-1), ethylene oxide 2-mole adduct (b1-1) of bisphenol A (trade name: New Pole BPE-20T, Sanyo Chemical Industries) 46.8 parts of 4,4′-diphenylmethane diisocyanate (a-1) (trade name: Millionate MT, manufactured by Tosoh Corporation) was charged and stirred at 100 ° C. in a nitrogen atmosphere. The mixture was reacted for 3 hours to obtain polyurethane (A-1) having an Mw of 40,000.

<Production Example 2>
46.8 parts of bisphenol A ethylene oxide 2-mole adduct (b1-1) was added to 74.3 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A and 4,4′-diphenylmethane diisocyanate (a-1). ) The same procedure as in Production Example 1 was carried out except that 40.6 parts were changed to 62.9 parts of 4,4′-diphenylmethane diisocyanate (a-1) to obtain a polyurethane (A-2) having an Mw of 94,000. It was.

<Production Example 3>
46.8 parts of bisphenol A ethylene oxide 2-mole adduct (b1-1) was added to 74.3 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A and 4,4′-diphenylmethane diisocyanate (a-1). ) The same procedure as in Production Example 1 was carried out except that 40.6 parts were changed to 59.0 parts of 4,4′-diphenylmethane diisocyanate (a-1) to obtain polyurethane (A-3) having Mw of 23,000. It was.

<Production Example 4>
46.8 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A was added to ethylene oxide adduct (b1-2) of bisphenol A (trade name: Newpol BPE-60, hydroxyl value 228, Sanyo Chemical Industries, Ltd. ) Made) Except having changed to 71.6 parts, it carried out similarly to manufacture example 1, and obtained the polyurethane (A-4) whose Mw is 48,000.

<Production Example 5>
46.8 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A was added to ethylene oxide adduct (b1-3) of bisphenol A (trade name: Newpol BPE-100, hydroxyl value 167, Sanyo Chemical Industries, Ltd. )) Except for changing to 97.7 parts, the same procedure as in Production Example 1 was carried out to obtain a polyurethane (A-5) having an Mw of 55,000.

<Production Example 6>
Production Example except that 40.6 parts of 4,4′-diphenylmethane diisocyanate (a-1) was changed to 27.3 parts of hexamethylene diisocyanate (a-2) (trade name: Duranate 50M, manufactured by Asahi Kasei Co., Ltd.) In the same manner as in Example 1, the reaction was performed for 10 hours to obtain a polyurethane (A-6) having an Mw of 40,000.

<Production Example 7>
Performed in the same manner as in Production Example 1 except that 40.6 parts of 4,4′-diphenylmethane diisocyanate was changed to 36.1 parts of isophorone diisocyanate (a-3) (trade name: VESTANAT IPDI, manufactured by Evonik). 10 hours Reaction was performed to obtain a polyurethane (A-7) having an Mw of 40,000.

<Production Example 8>
In a reaction vessel equipped with a stirrer, 100 parts of polyethylene glycol (b2-2) (PEG-4000N, manufactured by Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 3100, an ethylene oxide 2-mole adduct of bisphenol A (b1-1) 59.9 parts, 4,4′-diphenylmethane diisocyanate (a-1) 46.6 parts were charged and reacted for 3 hours with stirring at 100 ° C. under a nitrogen atmosphere to give a polyurethane having an Mw of 15,000 (A-8) Got.

<Comparative Production Example 1>
59.9 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A is added to 24.7 parts of ethylene oxide 2-mole adduct (b1-1) of bisphenol A, and 46.6 parts of 4,4′-diphenylmethane diisocyanate. Was performed in the same manner as in Production Example 8 except that 24.0 parts of 4,4′-diphenylmethane diisocyanate was changed to obtain polyurethane (A′-1) having Mw of 32,000.

<Example 1>
70 parts of the polyurethane (A-1) obtained in Production Example 1 and 30 parts of the aliphatic polyether polyol (b2-1) were charged into a reaction vessel equipped with a stirrer and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. As a result, a hot melt adhesive composition (E-1) was obtained.

<Example 2>
25 parts of polyurethane (A-2) obtained in Production Example 2, 74 parts of the above-mentioned aliphatic polyether polyol (b2-1) and phenolic antioxidant (F-1) (trade name: Irganox 1010, manufactured by BASF) ) 1 part was charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere to obtain a hot melt adhesive composition (E-2).

<Example 3>
75 parts of the polyurethane (A-1) obtained in Production Example 1, 20 parts of the aliphatic polyether polyol (b2-1), 4 parts of the polyethylene glycol (b2-2), the antioxidant (F- 1) 0.5 part and 0.5 part of a benzotriazole-based ultraviolet absorber (G-1) (trade name: TINUVIN 571, manufactured by BASF) are charged into a reaction vessel similar to that in Example 1, and at 100 ° C. in a nitrogen atmosphere. The mixture was stirred for 3 hours to obtain a hot melt adhesive composition (E-3).

<Example 4>
60 parts of the polyurethane (A-3) obtained in Production Example 3, 30 parts of the aliphatic polyether polyol (b2-1), 9 parts of the polyethylene glycol (b2-2), the antioxidant (F- 1) 0.5 part and 0.5 part of the ultraviolet absorber (G-1) described above were charged into the same reaction vessel as in Example 1 and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere to obtain a hot melt adhesive composition. (E-4) was obtained.

<Example 5>
70 parts of the polyurethane (A-4) obtained in Production Example 4 and 30 parts of the aliphatic polyether polyol (b2-1) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. And a hot melt adhesive composition (E-5) was obtained.

<Example 6>
70 parts of the polyurethane (A-5) obtained in Production Example 5 and 30 parts of the aliphatic polyether polyol (b2-1) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. And a hot melt adhesive composition (E-6) was obtained.

<Example 7>
70 parts of the polyurethane (A-6) obtained in Production Example 6 and 30 parts of the aliphatic polyether polyol (b2-1) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. And a hot melt adhesive composition (E-7) was obtained.

<Example 8>
70 parts of the polyurethane (A-7) obtained in Production Example 7 and 30 parts of the aliphatic polyether polyol (b2-1) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. And a hot melt adhesive composition (E-8) was obtained.

<Example 9>
65 parts of polyurethane (A-8) obtained in Production Example 8 and 35 parts of the above polyethylene glycol (b2-2) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. A melt adhesive composition (E-9) was obtained.

<Comparative Example 1>
20 parts of a styrene-butadiene-styrene block copolymer having a styrene content of 40% (trade name: TR-2000, manufactured by JSR Corporation), a hydrogenated product of a dicyclopentadiene copolymerized petroleum resin (trade name: Escorez E-5600 60 parts of ExxonMobil Co., Ltd., 5 parts of low molecular weight polyolefin (trade name: Viscol 660P, manufactured by Sanyo Chemical Industries), naphthenic process oil (trade name: Diana Process Oil NS-100, Idemitsu Kosan Co., Ltd.) 14 parts), 0.5 parts of the above antioxidant and 0.5 parts of phosphorus antioxidant (trade name: ADK STAB 2112, ADEKA Corporation) were mixed in the same manner as in Example 1 for comparison. Hot melt adhesive composition (E′-1) was obtained. The hot melt adhesive composition is a typical hydrophobic hot melt adhesive.

<Comparative example 2>
The polyurethane (A-1) obtained in Production Example 1 was used as a comparative hot melt adhesive composition (E′-2).

<Comparative Example 3>
26.7 parts of a lactone polyester polyol having a number average molecular weight of 500 obtained by ring-opening addition polymerization of ε-caprolactone to 2,2-dimethylolbutanoic acid in the same manner as in Example 1 of JP-A-2007-182515, and 2 -44.4 parts of a polyester polyol having a number average molecular weight of 2000 obtained by condensation reaction of butyl-2-ethyl-1,3-propanediol and adipic acid was mixed with a mixed solvent of 50 parts of dimethylformamide and a part of methyl ethyl ketone. By adding 3.0 parts of 1,4-butanediol to the mixed solvent and further adding 25.9 parts of diphenylmethane diisocyanate, the mixture is reacted at 80 ° C. for 3 hours to obtain a polyurethane resin solution (solid content 50.1). %).
The polyurethane resin solution was dried at 60 ° C. for 3 hours, and further dried at 110 ° C. for 3 hours under reduced pressure to obtain a comparative hot melt adhesive composition (E′-3).

<Comparative example 4>
60 parts of polyurethane (A′-1) obtained in Comparative Production Example 1 and 40 parts of the above polyethylene glycol (b2-2) were charged into the same reaction vessel as in Example 1, and stirred at 100 ° C. for 3 hours in a nitrogen atmosphere. A comparative hot melt adhesive composition (E′-4) was obtained.

The compositions of the hot melt adhesive compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 are summarized in Table 1. In the table, items not specifically described represent the number of copies.
Moreover, about the hot-melt-adhesive composition obtained in Examples 1-9 and Comparative Examples 1-4, T-type peeling strength, adhesiveness retention, and the contact angle of water were evaluated by the following methods, and the result Are listed in Table 1.

<T-type peel strength>
The present invention and a comparative hot melt adhesive were applied to a polypropylene nonwoven fabric having a length of 100 mm, a width of 25 mm, and a thickness of 100 μm in a 25 mm width in a bead shape (application temperature 150 ° C., application amount 0.2 g / m), and the same size. After bonding the cotton cloth, the sample was left for 24 hours in an atmosphere at 25 ° C. to obtain a T-piece peel strength evaluation test piece.
(1) Dry (Dry) State Using the tensile tester (Autograph AG-IS 1kN (manufactured by Shimadzu Corp.)), measure the peel strength at a tensile speed of 300 mm / min. T-type peel strength (dry) was set (N / 25 mm).
(2) Wet state in water (wet) Set the above test piece in a tensile tester, drop water on the cotton cloth with a dropper (about 3 to 5 drops), and the entire hot melt adhesive application part gets wet Put it in a state. After 30 seconds, the peel strength was measured at a tensile speed of 300 mm / min, and the maximum value was defined as T-type peel strength (wet) (N / 25 mm).

(Adhesive retention rate)
The adhesiveness retention was calculated from the following formula using the measurement result of the T-type peel strength.
Adhesion retention rate (%) = (T-type peel strength in wet state / T-type peel strength in dry state) × 100

About the hot melt adhesives obtained in Examples 1 to 6 and Comparative Examples 1 to 3, the melt viscosity at 150 ° C., the adhesiveness retention rate and the contact angle of water were measured by the following methods, and the results are shown. 1.

(Measurement method of melt viscosity at 150 ° C.)
It measured using the rotational viscometer (RB viscosity type viscometer, the Toki Sangyo company make) based on JISK7117-1: 1999. For the measurement, No. 4 rotor attached to the viscometer was used.

(Water contact angle measurement method)
Each of the hot melt adhesive compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 was heated and melted to 130 ° C., applied to a PET film with a thickness of 1.0 mm, and then cooled to room temperature. Then, a film-like adhesive layer was prepared and used as a contact angle measurement sample.
Using a fully automatic contact angle meter [Kyowa Interface Science Co., Ltd., PD-W], the contact angle between the contact angle measurement sample and water is measured in an environment of 25 ° C., and water droplets are applied to the surface of the contact angle measurement sample. The contact angle 0.5 seconds after dropping was measured.
When the contact angle between the adhesive layer and water is 0 to 60 degrees, the hot melt adhesive composition forming the adhesive layer is excellent in hydrophilicity and excellent in wettability with respect to the hydrophilic substrate. Therefore, the adhesive composition becomes a hot melt adhesive composition excellent in adhesive strength with a hydrophilic substrate.

As is clear from Table 2, the hot-melt adhesive compositions of the present invention (Examples 1 to 9) were wet with water and adhesiveness with a hydrophilic substrate as compared with the hot-melt adhesives of Comparative Examples. The adhesiveness is good. This is considered because the hot melt adhesive composition of the present invention has high hydrophilicity. Since the hot melt adhesive composition of the present invention contains the aliphatic polyether polyol (B), the melt viscosity at 150 ° C. is preferably low, so that the wettability with the base material is further improved, and under heating Spray coating is also possible.

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 and the like, and is particularly useful for adhesion to hydrophilic substrates such as paper and cloth. In addition, the adhesive strength can be secured even when the surface is wet, and the adhesive composition does not hinder the flow of water. It is suitable for bonding and fixing filters such as filter cloth and filter paper used for water treatment, and for bonding sanitary materials (disposable disposable diapers, sanitary products, etc.).

Claims (10)

A hot melt adhesive composition comprising a polyurethane (A) and an aliphatic polyether polyol (B), wherein (A) is a polyisocyanate (a), an aromatic diol (b1), and an aliphatic polyether A hot melt adhesive composition (E) which is a reaction product with polyol (b) containing polyol (b2), and the hot melt adhesive composition contains 45 to 70% by weight of oxyethylene groups based on the weight of the composition. ). The hot melt adhesive composition according to claim 1, wherein the aromatic diol (b1) is represented by the following general formula (1).
[Wherein, -Y- represents a direct bond or a methylene group, a dimethylmethylene group, a methylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, Z represents an alkylene group having 2 to 4 carbon atoms, and m and n are It is an integer greater than or equal to 1, and m + n is 2-100. ] The hot melt according to claim 1 or 2, wherein the aliphatic polyether polyol (b2) and the aliphatic polyether polyol (B) are each an alkylene oxide adduct of an aliphatic dihydric alcohol having 2 to 8 carbon atoms. Adhesive composition. The hot-melt adhesive composition according to any one of claims 1 to 3, wherein the aliphatic polyether polyol (b2) and the aliphatic polyether polyol (B) are the same. The hot melt adhesive composition according to any one of claims 1 to 4, wherein the polyurethane (A) has a weight average molecular weight of 10,000 to 150,000. The hot melt adhesive composition according to any one of claims 1 to 5, wherein an isocyanate group content of the polyurethane (A) is 0.02% or less based on the weight of the polyurethane (A). The hot melt adhesive composition according to any one of claims 1 to 6, wherein a weight ratio of the polyurethane (A) to the polyether polyol (B) is 90/10 to 10/90. The hot melt adhesive composition according to any one of claims 1 to 7, wherein the melt viscosity at 150 ° C is 0.1 to 10 Pa · s. The hot-melt adhesive composition according to any one of claims 1 to 8, wherein a contact angle of water with respect to the hot-melt adhesive composition (E) measured by a droplet method is 0 to 60 degrees. The adhesive body which has an contact bonding layer which consists of a hot-melt-adhesive composition (E) in any one of Claims 1-9.