JPS60135472A - Adhesive for polyester material - Google Patents

Abstract

PURPOSE:To provide an adhesive compsn. which exhibits excellent adhesion to polyester materials over a long period of time, by blending a reaction product between a specified polyester polyol and a diisocyanate, a curing agent and said polyester polyol. CONSTITUTION:A reaction product obtd. by reacting a polyester polyol (a) having a m.p. of 40 deg.C or below and an MW of 500-3,000 obtd. from the polycondensation reaction of two or more dibasic acids with a glycol (or a dibasic acid withtwo or more glycols) with an org. isocyanate (b) such as isophorone diisocyanate in a molar ratio of 1:0.9-1, is used. 1-8pts.wt. curing agent such as Coronate HL (a product of Nippon Polyurethane Kogyo K.K.) and said polyester polyol [component (a)] are blended with 100pts.wt. said reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to an adhesive suitable for use in polyester base materials such as fibers and films.

(Prior art) Polyester materials have excellent properties such as toughness, durability, and chemical resistance, but there are problems with their adhesive properties, and although various adhesives have been proposed, An adhesive with satisfactory stability has not yet been found.

For example, thermoplastic copolymer polyester adhesives are known as adhesives for polyester materials, especially polyethylene terephthalate films and cloth, but although the adhesive strength is satisfactory to some extent, the adhesive stability deteriorates over time. A decrease in power was observed. Various polyurethane adhesives are also known, but like polyester adhesives, they have problems with adhesive stability. (Refer to Japanese Patent Publications ShojO-Fuhei No. 22, No. 311-/≠73) (Object of the Invention) The present invention provides an adhesive that exhibits excellent adhesive strength to the polyester material and maintains adhesive strength for a long period of time. This provides an adhesive with excellent stability.

(Structure of the Invention) The present invention can be summarized as follows: At least one of the dibasic acid component and the glycol component constituting the A polyester polyol is obtained by reacting two or more kinds of compounds, and
1 mole of polyester polyol having a melting point of
This is a polyester material adhesive which contains as an active ingredient a reaction product obtained by reacting Oy to 10 moles of organic diisocyanate compound B, and further contains a curing agent and the polyester polyol (component A).

The present invention applies a curing agent and the above-mentioned specific polyester polyol to a reaction product obtained by reacting a polyester polyol that is obtained from a composition of specific components and has a melting point of 0° C. or lower and an organic diisocyanate. This was completed based on the knowledge that a composition containing the following compounds exhibits excellent adhesion to polyester materials.

To explain the present invention in more detail, the specific polyester polyol used in the present invention is produced by reacting two or more compounds with at least one of the dibasic acid component and the glycol component that constitute the polyester polyol. and has a melting point of 0.degree. C. or lower.

That is, the polyester polyol of the present invention is produced by condensation polymerization of two or more types of dibasic acids and seven types of glycols or by condensation polymerization of seven types of dibasic acids and two or more types of glycols. However, in the present invention, a polyester polyol having a melting point of ≠0° C. or less must be obtained by a selected combination of a dibasic acid component and a glycol component, and this must be used.

The molecular weight of the polyester polyol used in the present invention is
SOO~3000 is suitable.

The dibasic acid components used in the production of the polyester polyol include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahedral heptalic anhydride, and hexahydrophthalic anhydride. , tetrabromophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, etc.

On the other hand, glycol components include ethylene glycol,
Examples include fluoropylene gellicol, 3-ethylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, and hydrogenated bisphenol A.

By selecting and combining these components and conducting condensation polymerization,
A polyester polyol having a melting point ψ0°C or less is obtained. Some such polyester polyols are commercially available.

The obtained polyester polyol has an 10H group or a -000H group at the end, and this is reacted with the incyanate group of the organic diyn7anate compound to produce polyurethane. The reaction molar ratio of the polyester polyol and the organic diincyanate compound is suitably such that the organic diincyanate compound is reacted at a ratio of 0 to 0 mol per 1 mol of the polyester polyol.

When the organic diincyanate compound is less than 0.2 moles,
The adhesive has low film strength and adhesive strength, which is undesirable.

On the other hand, if the organic diincyanate compound is used in an amount greater than tO moles and the chain is extended with a diol or diamine, the film becomes non-adhesive and the adhesive strength becomes low, which is not preferable.

The reaction between the polyester polyol and the organic diiso/anate compound may be carried out in the same manner as a normal urethane reaction. For example, the polyester polyol and the organic diisocyanate are placed in a reaction vessel and heated for 10 minutes under a nitrogen stream.
Heat and stir at ~0°C for 2≠ hours in the evening. Since the viscosity increases during the reaction, it is necessary to adjust the viscosity to an appropriate level by adding an organic solvent.

The resulting polyurethane still contains free 10H groups or -C
Since it has an OOH group, it is crosslinked using a polyisocyanate curing agent.

Examples of the organic cyinone anate compound to be reacted with this polyester polyol include aliphatic diisocyanates such as hexamethylene diinosoanate, trimethylhexamethylene diisonoanate, 2t-lysine diisocyanate, etc.; 2μ-tolylenediin 7anate, 2.
Aromatic diiso/anates such as 1-tolylene diisocyanate, m-quinolylene diisocyanate, etc., and hydrogenated compounds of these aromatic diisocyanates,
Alicyclic diisocyanates such as inophorone diisocyanate can be used.

As the organic solvent, N,N-dimethylformamide, dimethylsulfoxide, dimethylacetamide, N,N
- Diethylformamide, diethylacetamide, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, toluene, xylene, ethyl acetate, butyl acetate, etc. can be used.

The adhesive of the present invention contains the reaction product obtained above as an active ingredient, but when using it, it is necessary to add and blend a curing agent.

As the curing agent, there is a polyisocyanate compound, and it is appropriate to add the compound in an amount of /~g parts by weight per 10[theta] parts by weight of the reaction product.

As the polyincyanate compound, an aliphatic, aromatic or alicyclic compound having one or more isocyanate groups in the molecule is used, and generally commercially available yellowing type or non-yellowing type polyisocyanates are used. If available, any of them can be used; for example, product names Sumitur L1 Sumitur N, (manufactured by Sumitomo Bayer), Takene) D-/#7N (manufactured by Kurade Pharmaceutical Co., Ltd.), Coronate HL,
Examples include Coronate L (manufactured by Nippon Polyurethane Industries).

In addition, in order to impart tackiness to the adhesive itself and further improve various performances of the adhesive, the above-mentioned specific polyester polyol was added to the resin solid content of the reaction product of 700 parts by weight.
It is appropriate to add up to 30M parts. This is because if the amount exceeds 30 parts by weight, the adhesive strength will be poor at the initial stage of adhesion.

The adhesive of the present invention not only exhibits excellent adhesive strength to polyester materials, but also has excellent water resistance, weather resistance, heat resistance, flexibility, etc.

Examples are shown below to more specifically explain the present invention.

To polyurethane solution! Il! I# Polyester polyol liquid at room temperature (trade name 7 Decanyu Ace F /2/2- +22: molecule [-/7g λ manufactured by Asahi Denka Kogyo Co., Ltd.) /, 200 parts (tamol in θ), isophorone diisocyanate ) /170 parts (0.3 moles)
A small amount of dibutyltin dilaurate and a small amount of dibutyltin dilaurate as a catalyst were placed in a reaction vessel and reacted for 10 hours at 70-♂O℃ under a nitrogen stream, and then ethyl acetate was added to prepare polyurethane solution A in which the resin solid content was ≠ O. .

Examples/~Co: To 100 parts of the polyurethane solution A, a polyisocyanate compound (trade name: Coronate HL,
Nippon Polyurethane Kogyo Co., Ltd.)/Hirobe added (Example/), and to this, polyester polyol (trade name ADEKA NEW ACE F/, 2/, 2-λ, manufactured by Mudenka Kogyo Co., Ltd.) ethyl acetate. Solubility (resin solid content HiroO weight%)
In Example 2), an adhesive was prepared by adding 77 parts.

Preparation of polyurethane solution B Polyester polyol with a melting point of 30°C (trade name: Adeka 221 Ace V-Bar 90: Molecule-1 #/20 manufactured by Asahi Denka Kogyo Co., Ltd.) 7200 parts (0, J 26 mol), inphorone diisocyanate /JIr part (02.22 mol) and a small amount of diptyltin dilaurate as a catalyst were placed in a reaction vessel and reacted under a nitrogen stream at 70~0°C for /S hours, and then diluted with ethyl acetate to make the resin solid content ≠ 0. A polyurethane bath liquid B having a weight of ik% was prepared.

Example 3 ~ ≠ To 700 parts of the polyurethane solution B, a polyincyanate compound (trade name: Coronet HL) was added as a curing agent.
Nippon Polyurethane Kogyo Co., Ltd. v)/≠ part (Example 3), and further added an ethyl acetate solution (resin solid) of polyester polyol (trade name Adeka New Ace V -/≠-90 manufactured by Mudenka Kogyo Co., Ltd.) min ψO weight%)/
Add z part (, (Example tl) to the adhesive!Ii-wL.

Preparation of polyurethane solutions C-F Polyurethane solutions C and F were prepared by reacting isophorone diisocyanate with the polyester polyol shown in Table 1 in the same manner as in the preparation of polyurethane solutions.

Comparative Example/~Ko polyurethane solution C-F was added with a curing agent shown in Table 2 and an ethyl acetate solution of polyester polyol (resin solid content).
≠O wt %) was added to prepare the adhesive.

Table 2 Application Examples Examples/~≠ and Comparative Examples/~Each adhesive obtained in
Is the solid content 0r/n? After applying it to a polyethylene terephthalate film and pre-drying it for 7 minutes at 0°C to 0°C, it was laminated with polyethylene terephthalate cloth and heated at 710 to 720°C for 30°C. A load of /crl was applied to the bonding.

The adhesive strength of the test pieces was measured after being left at room temperature for 2 hours, 7 days, and 3 months, and the results are shown in Table 3.

In addition, with respect to water resistance, weather resistance, heat resistance, and flexibility, the adhesives of Examples/-Hiro gave good results in all items.

To measure the adhesive strength, a specimen with a width of 3 crn and a length of 3 cm was attached to a tensile tester (trade name: Autograph Ryotsu Seisakusho Co., Ltd.), and the tensile results were obtained at a tensile speed of jOwIlZ.

From this result, it is clear that the adhesive with the composition of the present invention maintains excellent adhesive strength even over time.

Claims (1)

[Claims] / At least one of the dibasic acid component and the glycol component constituting the A polyester polyol is 2
Obtained by reacting more than one species of compounds, and ≠
Contains as an active ingredient a reaction product obtained by reacting 1 mol of polyester polyol having a melting point of θ°C or less with 09 to 10 mol of B organic diisocyanate compound,
A polyester-based adhesive further comprising a curing agent and the polyester polyol (component A). The polyester material adhesive according to claim 1, wherein the curing agent is a polyisocyanate compound containing two or more iso/anate groups in the molecule. 3. The polyester adhesive according to claim 7, wherein the polyester polyol is added in an amount of 30 parts by weight based on 100 parts by weight of the resin solid content of the reaction product. ≠ The amount of curing agent added is 700% of the resin solid content of the reaction product.
The polyester material adhesive according to claim 1, wherein the polyester material adhesive ranges from / to ♂ parts by weight based on parts by weight.