JPH03162477A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in creep performance, giving good heat-resistant creep performance, suitable for water-based adhesion for PVC-based base materials, comprising an aqueous solution of a hydroxyl group- contg. urethane resin and an organometallic coordination compound. CONSTITUTION:The objective composition comprising (A) an aqueous solution of a hydroxyl group-contg. urethane resin (e.g. prepared by dissolving in water a NCO-terminated urethane prepolymer containing hydroxyl group which can be produced from an active hydrogen compound, a organic polyisocyanate and a compound having both active hydrogen and anionic group, etc.) and (B) an organometallic coordination compound (e.g. aluminum trisacetylacetonate).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition suitable for water-based adhesion for polyvinyl chloride-based substrates.

[Conventional Technology] Composite materials made by bonding plywood and polyvinyl chloride sheets have been used for building materials and the like. Compositions consisting of water-based polyurethane and ethylene/vinyl acetate copolymer emulsion are generally known as adhesives (for example, Japanese Patent Publication No. 81
(No. 80109) [Problems to be Solved by the Invention] However, the above composition has poor creep performance, which causes a problem in that blistering occurs in polyvinyl chloride during use.

[Means for solving the problem] As a result of intensive research in view of the current situation, the present inventors have found that:
We have arrived at the present invention.

That is, the present invention... This is an adhesive composition comprising a hydroxyl group-containing urethane resin aqueous liquid (A) and an organometallic coordination compound (B).

The hydroxyl group-containing urethane resin aqueous solution (A) used in the present invention contains an active hydrogen compound, an organic polyisocyanate, an active hydrogen and an anion group or an anion-forming group (one that reacts with a base to form an anion group). (in this case, converted into anionic groups by neutralization with a base before, during or after the urethanization reaction) and an NGO-terminated urethane prepolymer containing hydroxyl groups obtained from a compound containing hydroxyl groups is added to water. Obtained by dissolving or dispersing in water, or NGO
Examples include those in which a terminal urethane prepolymer is dissolved or dispersed in water containing an extender, and hydroxyl groups are contained in the water.

Anionic groups or anion-forming groups Examples of the anionic groups in the compound include salt-type groups such as a canoleboquinole group, a snolefonic acid group, and a phosphoric acid group. Examples of the salts forming the salt-type groups include alkali metal salts (sodium salts, potassium salts, etc.). ), ammonium salts and amine salts (trimethylamine salt, triethylamine salt, etc.). Examples of the anion-forming group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, a phosphine group, a carboxyl anhydride group, a sulfonic anhydride group, a phosphoric ester group, and the like.

Compounds containing active hydrogen and anionic groups or anion-forming groups are known (e.g.
24192, JP 52-3438, JP 55-41Ei07, and JP 63-145
318 Publication) can be widely used, such as hydroxycarboxylic acids (glyceric acid, glycolic acid, 2,8-dioxybenzoic acid, dimethylolpropionic acid, etc.), hydroxysulfonic acids [2-hydroxyethanesulfonic acid, phenolic acid, etc.] Norefonic acid-(2), Naftho! each isomer of resnorefonic acid, 3-(2,3-dihydroxyproboxy)-1-propanesulfonic acid sodium salt, etc.],
Ami-7 carboxylic acid (glycine, 6-aminocaproic acid,
isomers of mono- and di-aminobenzoic acid), aminosulfonic acids (amidesnorefonic acid, hydrazine-disulfonic acid, taurine, etc.), esters of phosphoric acid [bis-(α-hydroxyisopropynolyl) monophosphinic acid, monophosphorous acid, Bis-glycol ester, mono-bis-propylene glycol ester, etc.).

As a base that converts an anion-forming group into an anion group,
Examples include inorganic bases (eg, sodium hydroxide, potassium hydroxide, etc.), and organic bases (eg, trimethynoleamine, triethynoleamine, tributynoleamine, diethanolamine, etc.).

Examples of active hydrogen compounds include high molecular polyols, low molecular polyols, and polyamines.

Examples of high-molecular polyols include polyether polyols {low-molecular polyols (ethylene glycol, propylene glycol, 1, 3- or 1, 4-butanediol, 3-
Bifunctional polyols such as methylpentanedionole, 1,6-hexanethiol, neopentyl glycol, diethylene glycol, cyclohexylene glycol;
Trifunctional or higher functional polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, polyhydric phenols (bisphenols such as bisphenol A), and amines (
alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine; aliphatic polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine; aromatic diamines such as trilenediamine, diphenylmethanediamine, etc.)
alkylene oxide [alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide,
Adducts of one or more types (random and/or block) such as butylene oxide, ring-opening polymers of alkylene oxide (polytetramethylene ether glycol, etc.), polyester polyols [polycarboxylic acids (aliphatic polycarbonate, etc.) Acids such as adipic acid, succinic acid, sebacic acid, acelaic acid, fumaric acid, maleic acid and diallinated linoleic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid) and polyether polyols. Polyester polyols with a hydroxyl group at the end of low molecular weight polyols or low molar adducts (diethylene glycol, triethylene glycol, etc.) of anolekylene oxide (ethylene oxide, propylene oxide, etc.), lactone polyesters (polycaprolactone diol, etc.),
[polycarbonate diol, etc.], polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol, polymer polyol [polyol made by polymerizing pinyl monomer (acrylonitrile, styrene, etc.) in a polyol (the above-mentioned polyether polyol, polyester polyol, etc.)], etc. Examples include mixtures of two or more of these.

Among the polymer polyols, preferred are polyester polyols.

The OH equivalent of the polymer polyol is usually 200 to 3000,
Preferably it is 250-2000.

Examples of the low-molecular polyol include those similar to the low-molecular polyols described in the section on polyether polyols. Preferred low molecular weight polyols are ethylene glycol and 1.4-butanediol.

Examples of polyamines include hexamethylene diamine, isophoronoamine, xylylene diamine, diphenylene diamine, and the like.

Among these active hydrogen compounds, preferred are high-molecular polyols alone or a combination of high-molecular polyols and low-molecular polyols.

The weight ratio of high molecular polyol to low molecular polyol and/or polyamine is usually 1:0 to 1:5, preferably 1:0 to 1:3. The average active hydrogen (OH, NH2, NH, etc.) equivalent of the active hydrogen compound (total) is usually 70-2000, preferably 100-! 30G
It is.

The average number of functional groups of the active hydrogen compound is usually 2 to 3, preferably 2 to 2.5.

Examples of the organic polyisocyanate include aliphatic polyisocyanates having 2 to 12 carbon atoms (excluding the carbon in the NGO group), such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI).
}, dodecamethylene diisocyanate, l.6.11-
Undecane triisocyanate, 2,2,4-trimethynolehexane diisocyanate, lysine diisocyanate, 2,G-diisocyanate methyl caproate, bis(2-incyanate ethyl) fumarate, bis(2
-isocyanate (P-toethyl) carbonate, 2-incyanate ethyl-2,6-diisocyanate hexanoate, etc.; alicyclic polyisocyanate having 4 to 15 carbon atoms,
For example, inphorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI),
Cyclohexylene diisocyanate, methyl hequine diisocyanate (hydrogenated TDI) bis(2-incyanate ethyl) 4-cyclohexene-1,2-dicarpoxylate, etc.; aromatic aliphatic polyisocyanates having 8 to 12 carbon atoms, such as xylylene diisocyanate Isocyanate, tetramethylxylyleneneusonanate, diethynolebenzene diisocyanate, etc.; water modified product of HDI, IPDI
and MDI Sankeika; aromatic polyisocyanates having 6 to 20 carbon atoms, such as tolylene diisonane} (T
DI), crude TDI1 diphenylmethane diisocyanate (MDI) polyphenylmethane polyisocyanate (PAPI; crude MDI), naphthylene diisocyanate, etc.; and modified products of these polyisocyanates (
Carbodiimide group, uretdione group, uretimine group,
Biuret group-containing and/or incyanurate group-containing modified products, etc.) can be used. Preferred among these are brush D1, IPDI, TDI and MDI.

In producing NGO-terminated urethane prebomer,
Although the ratio of the active hydrogen-containing compound (including active hydrogen compounds and compounds containing active hydrogen and an anionic group or anion-forming group) and the organic polyisocyanate can be varied, the equivalent ratio of the active hydrogen group to NGO is Usually 1:1.01 to 1:2, preferably 1:1
．． 02-1: 1.7.

The amount of the compound containing active hydrogen and an anionic group or anion-forming group to be used is such that the content of the anionic group or anion-forming group is usually 0.1-10% based on the resin content of the final hydroxyl group-containing urethane resin aqueous liquid. The amount is preferably 0.5 to 8% by weight.

In producing NGO-terminated urethane prepolymer,
The active hydrogen-containing compound and the organic polyisocyanate may be reacted at once or in stages [a part of the active hydrogen-containing compound (for example, a polymeric polyol) and an organic polyisocyanate are reacted to form an NGO-terminated urethane preform. A method in which the remaining active hydrogen-containing compound is reacted after forming a remer] may also be used.

The NGO-terminated urethane prepolymer formation reaction typically involves 40
-140"C1 Preferably carried out at 60-120°C (however, when reacting polyamine, it is usually 80"C)
C or less, preferably at a temperature of 0 to 70"C).

The reaction may be carried out in a solvent (eg, acetone, toluene, nomethylformamide, etc.) and may be added during or after the reaction.

When a compound containing an anion-forming group is used in the NGO-terminated urethane brevolomer, it is treated with an organic or/and inorganic base to convert at least a portion of the compound into an anionic group.

The hydroquine group-containing urethane resin aqueous liquid (A) is usually (!) added to the NGO-terminated urethane polymer obtained by the above method, and added with a polyol (as described in the section on polyether polyol) in such a proportion that hydroxyl groups are in excess. (2) Adding a hydroxyl group-containing amine compound (diethanolamine, aminoethylethanolamine) to the NGO-terminated urethane prepolymer obtained by the above method as an extender. (3) When the NGO-terminated urethane prebolimer obtained by the above method is dissolved or dispersed in water, a hydroxyl group-containing amine compound is used as an extender. (diethanolamine, aminoethylethanolamine, etc.) and amine elongation.

In addition, a pure aqueous hydroxyl group-containing urethane resin liquid can be obtained after the used solvent is removed by distillation or the like.

The hydroxyl group content of the hydroxyl group-containing urethane resin aqueous liquid (A) is usually 0.01 to 10% by weight based on the resin content of the final hydroxyl group-containing urethane resin aqueous liquid,
Preferably 0. It is 5% by weight.

Examples of the organometallic coordination compound (B) include organoaluminum coordination compounds such as aluminum trisacetylacetonate and aluminum triisopropoxide; organic zirconium coordination compounds such as zirconium tetrakisacetylacetonate and diisopropoxyzirconium bisacetylacetonate; compounds, organic titanium coordination compounds such as titanium tetrakis acetylacetonate, diisopoxytitanium bisacetylacetonate, and the like.

Among these, preferred are organoaluminium coordination compounds and organotitanium coordination compounds.

The amount of the hammer metal coordination compound (B) can be blended in any proportion to the resin content of the final hydroxyl group-containing urethane resin aqueous liquid, but the solid content is usually 0.0!
~10ffIffi% dish.

The adhesive composition of the present invention can contain an aqueous resin, a solvent, an inorganic filler, a binder, and the like, if necessary.

Examples of the aqueous resin include acrylic acid-based, vinyl acetate-based, vinyl chloride-based, urethane-based emulsion SBR, NBR-based latex, and the like.

Examples of the solvent include toluene, butyl cellosol, butopropyl alcohol, and the like.

Examples of inorganic fillers include calcium carbonate, silica, talc, and glass fiber.

Thickeners include cellulose derivatives, starch derivatives,
Examples include polyacrylic acid derivatives and polyvinyl alcohol.

Other additives include dispersants, protective colloids, preservatives,
Examples include antifreeze agents, antifoaming agents, and various stabilizers for improving light resistance and heat resistance.

The adhesive composition of the present invention can be used as an adhesive for polyvinyl chloride-based adhesives and the like.

The adhesive composition of the present invention is suitable not only for adhering polyvinyl chloride-plywood, but also for adhering polyvinyl chloride to each other and other substrates (for example, cloth, paper, metal, plastic, etc.). It can also be used as an adhesive for cloth, paper, metal, plastic, etc.

The amount of the adhesive composition of the present invention used is usually 1 to 1000 g.
/4 Preferably 5 to 500 g//.

The adhesive composition of the present invention can be applied using a roll coater, knife coater, etc., which are commonly used in this field.
Examples of methods include spray coating.

A coated product of the adhesive composition of the present invention can be bonded at room temperature or by heating, usually at room temperature to 200°C. The curing time is 1 to 10 days at room temperature, and shorter under heating, for example, 1 to 20 minutes at 60 to 200°C.

The coated material of the adhesive composition of the present invention can be cured at room temperature or by heating, and can be cured by pressing, for example, by a commonly used method such as a pressing roller press.

[Example] The present invention will be further explained with reference to Examples below, but the present invention is not limited thereto. In Examples and Comparative Examples, "parts" indicate parts by weight, and "%" indicate weight %.

Examples 1 to 3 In a pressure polymerization vessel equipped with a thermometer and a stirrer, 319.8 parts of polyethylene adipate (molecular weight 2000), 3 parts of dimethylolpropionic acid 14, 64.9 parts of tolylene diisocyanate, and acetone were placed. After charging 400.0 parts and purging the reaction system with nitrogen gas, the reaction was carried out at 80°C for 7 hours with stirring to produce NC with an NGO% content of 1.02'A.
An acetone solution of O-end EiJ urethane prebolimer was obtained.

This was cooled to 30°C or less and triethylamine 3.
Added 7 parts.

Next, aminoethylethanolamine! ．． 0 parts and water 8
00.0 parts of the mixture was added to the acetone solution, and then the acetone was removed under reduced pressure at below 70°C to obtain a solid content of 40.5%.
, 987.7 parts of a hydroxyl group-containing water-dispersible urethane resin aqueous solution (A-1) having a viscosity of 750 cp/25°C was obtained.

Next, an adhesive composition of the present invention was prepared using the following formulation. In the following, diisopropoxybis(acetylacetonato)titanium (Nippon Soda K.K.
．． In Example 1, dihydroxypis(lactato) titanium monoammonium salt (Japanese soda i) was used.
1K. KJ! Example 2 uses aluminum monoacetylacetonate bis(ethyl acetoacetate) (Kawaken Fine Chemicals K.K.
．． Example 3 used W aluminum chelate D).

(A-1), 50 parts of EVA Emulsin B (Sumiyuki Flex 400 manufactured by Sumitomo Chemical Industries K.K.), and 2.5 parts of an organometallic coordination compound were blended, and a thickener (Nippon Acrylic Chemical K. The viscosity was adjusted to 10,000 to 20,000 cp using Brimal ASE-80 (manufactured by K. K.) to obtain an adhesive composite of the present invention.

Comparative Example 1 A comparative adhesive composition was obtained by blending 50 parts of (A-1) and 50 parts of EVA emulsion, and adjusting the viscosity to 1 to 20,000 cp with a thickener.

Comparative Example 2 320.7 parts of polyethylene adipate (molecular ffi 2000) was placed in a pressure polymerization vessel equipped with a thermometer and a stirrer.
After charging 14.3 parts of dimethylolpropionic acid, 65.0 parts of tolylene diisocyanate, and 400.0 parts of acetone, and purging the reaction system with nitrogen gas, the mixture was stirred for 80"
C for 7 hours containing NCO% [1.04% NGO
An acetone solution of the terminal urethane prepolymer was obtained.

Cool this material to below 30°C and add triethylamine 9.
．． Added 7 parts.

Next, 0.0 part of water GO was added to the acetone solution, and then the acetone was removed under reduced pressure at 70° C. or below, and the solid content was 39.
Hydroxyl group-containing water-dispersible urethane resin aqueous solution (A-2) 8%, viscosity 510 cp/25°C 100
5.0 parts were obtained.

Next, the following formulations were created. (A-2) 50 parts, EVA emulsion a 50 parts, diisopropoxypis (
A comparative adhesive composition was obtained by blending 2.5 parts of titanium (acetylacetonate) and adjusting the viscosity to 10,000 to 20,000 cp with a thickener.

Obtained adhesive compositions (Examples 1-3, Comparative Examples 1-2)
The evaluation results of heat resistance creep and peel strength are shown in Table 1.

Table-1 Evaluation method 1. Preparation of test piece: On a soft polyvinyl chloride root (20 x 12 cm),
The adhesive composition was applied with an applicator to a concentration of 90 g/m2, and plywood (20 x 12 cm) was attached. 40
After crimping at kg/m2 for one day, it is cured at room temperature for six days.

2. Cut the heat-resistant creep test specimen into a width of 2.5 cm (length of 12 cm),
Apply a load of 500g to the tip of the polyvinyl chloride,
The peeled length is measured after 1 hour in an atmosphere of °C.

3. Cut the peel strength test specimen to a width of 2.5 cm + (length 12 cm), and test it with the peel tester at a knob moving speed of 200 mm/min.
Measure the peel strength at 5°C.

[Effects of the Invention] However, since the above composition has poor creep performance, blistering occurs on polyvinyl chloride during use. 8m
It becomes.

The adhesive composition of the present invention has superior creep performance compared to conventional adhesive compositions and exhibits good heat-resistant creep performance. No blistering occurs on polyvinyl chloride during use.

Since it exhibits the above effects, a composite material made by laminating plywood and polyvinyl chloride sheet with this composition can be widely applied to building materials, furniture, etc.

Claims (1)

[Claims] 1. An adhesive composition comprising a hydroxyl group-containing urethane resin aqueous liquid (A) and an organometallic coordination compound (B).