JPS62250051A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a polyurethane resin and a urethane-modified epoxy resin, having excellent durability such as heat- resistance, water-resistance, etc., as well as excellent adhesivity to metal, plastic, etc., and suitable especially as an adhesive. CONSTITUTION:The objective resin composition can be produced by compounding (A) a polyurethane resin having a number-average mol.wt. of 10,000-300,000, preferably 30,000-200,000 and produced by reacting a polyhydroxyl compound and a low-mol.wt. organic diol with an organic diisocyanate at a molar ratio of 0.95:1-1:0.95 with (B) a urethane-modified epoxy resin produced by reacting (i) an epoxy resin having an epoxy equivalent of preferably 100-4,000 and containing hydroxyl group in the molecule, e.g. an epoxy resin containing at least one substituted or unsubstituted glycidyl ether group on an average in a molecule with (ii) a compound having isocyanate group at a (hydroxyl group):(isocyanate group) ratio of 10:1-1:1.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a resin composition.

Specifically, it is a resin composition consisting of polyurethane resin (I) and urethane-modified epoxy resin (candy), and has excellent adhesion to a wide range of adherends such as reeds, especially metals, plastics, and wood as an adhesive. This resin composition also has excellent durability such as heat resistance and water resistance.

[Conventional technology]

It is well known that solutions of polyurethane resins dissolved in solvents are widely used as adhesives for bonding various adherends.

In this case, the IJ urethane resin that can be used because of the restriction that it is soluble in a solvent must be a linear polymer with little branching. For this reason, when used alone, its use is severely limited not only by its low adhesive strength but also by its durability, particularly heat resistance and water resistance.

A common solution to this problem is to use isocyanate compounds as curing agents. The isocyanate compound mentioned here is typically triphenylmethane triisocyanate (trade name: De 87ur RJ). This isocyanate compound is added with the expectation that it will react with the urethane bonds in the polyurethane resin to form allophanate bonds and make it three-dimensional. This does not sufficiently solve the problem in terms of durability.

[Problem that the invention seeks to solve]

In order to improve these drawbacks, a mixed system of polyurethane resin and epoxy resin containing hydroxyl groups in the molecule has been studied. In this case, when the hydroxyl group content in the epoxy resin is increased, the incyanate compound used as a curing agent selectively reacts with the hydroxyl groups, and conversely becomes a factor that inhibits crosslinking with the polyurethane resin. For this reason, the amount of epoxy resin added is severely restricted, and it is difficult to add enough epoxy resin to actually confirm the effect of adding epoxy resin. Conversely, if the hydroxyl group content of the epoxy resin is kept low, the number of crosslinking points in the epoxy resin will decrease, and durability such as heat resistance will not be improved.

In order to improve these drawbacks, the present inventors completed the present invention as a result of intensive research with the aim of obtaining a resin composition that has excellent adhesive strength as well as particularly durability such as heat resistance and water resistance. I ended up doing it.

[Failure to solve the problem]

That is, the present invention provides a urethane modified product obtained by reacting a polyurethane resin (I), an epoxy resin (II-1) containing a hydroxyl group in the molecule, and a compound (II-b) containing an isocyanate group. The object of the present invention is to provide a resin composition comprising a 1-oxyresin (II) and having excellent heat resistance, water resistance, durability, and adhesiveness.

The urethane resin (r) used in the present invention includes a hydroxyl group-containing component consisting of a polyhydroxy compound (T1) and a low molecular weight organic diol (I-b), and an isocyanate group-containing component consisting of an organic diisocyanate (I-c). The polyhydroxy compound (I-a) preferably has a number average molecular weight of 10,000 to 300,000, and particularly preferably has a number average molecular weight of 30,000 to 200,000. 600 to 3,000, and includes, for example, various polyester polyols or polyether polyols used in the production of general urethane compounds. The polyester polyol mentioned here includes a dehydrated mesh or transesterification reaction product of polyhydric alcohol and polybasic carboxylic acid, a dehydrated mesh or transesterification of hydroxycaldic acid and polyhydric alcohol, etc. The polyhydric alcohol used is, for example, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol,
Examples of the polybasic carboxylic acids include adipic acid, Geltal acid, azelaic acid, succinic acid, succinic anhydride, sepacic acid, fumaric acid, maleic acid (aliphatic dibasic acid component), phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, tetrachlorophthalic anhydride, tetrachlor Terephthalic acid,
Phthalic anhydride, orthophthalic acid, kiphthalic acids, esters of alcohols of phthalic acid, and phthalic anhydride (
Examples include aromatic dibasic acid component (hereinafter referred to as aromatic dibasic acid component), dimer acid, and pyromellitic acid. Also useful as condensates of hydroxycarboxylic acid and polyhydric alcohols are castor oil, and reaction products of castor oil and ethylene glycol, propylene glycol, and the like. Furthermore, polyols and precursors obtained by ring-opening polymerization of lactones such as caprolactone can use natediols. Examples of polyether polyols include one or more alkylene oxides such as ethylene oxide, tetrapyrene oxide, butylene oxide, and tetrahydrofuran.
It is a product obtained by addition polymerization with a compound having two or more active hydrogen atoms, and any of the known thiliether preols used in the production of ordinary preurethane resins can be used. In this case, examples of compounds having two or more active hydrogens include the above-mentioned polyhydric alcohols, polybasic carganic acids, amines such as ethylenediamine and hexamethylenediamine, ethanolamine, propatoolamine, etc. Examples include alkanolamines, resorcinol, polyhydric phenols such as bisphenol, and castor oil. Among these, it is particularly preferable to use polyester polyols.

The low molecular weight organic diols (I-b) preferably have a number average molecular weight of 60 to 400, and difunctional ones among the above-mentioned polyhydric alcohols can be used. The ratio of this low molecular weight organic diol (I-b) to the above-mentioned I-hydroxy compound (ia”) is (Le-a):(I-b)=
It is desirable that the ratio is 1:s to 1:0.

As organic diisocyanate (I-(I), various compounds used in the production of ordinary polyurethane resins can be used, such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate), 1 .5-naphthalene diisocyanate, dicyclohexylmethane diisocyanate (hydrogenated ■■), and the like.

The polyurethane resin (I) of the present invention comprises a hydroxyl component consisting of a polyhydroxy compound (1) and a low molecular weight organic diol (I-b) and an isocyanate component consisting of an organic diisocyanate (I-(RI) at a molar ratio of 0.95. :1.00
~1.00:0.95. Preferably Q, 98:1.
It can be obtained by reacting at a ratio of 0.00 to 1.00:0.98.

The polyurethane resin (I) of the present invention may be produced in a solvent-free system or in a solution state.

The urethane resin (I) produced in a solvent-free manner is used after being dissolved in an organic solvent.

Solvents that can be used in the present invention include dimethylformamide, toluene, xylene, benzene, dioxane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloromethane, 1,1.
1-) A single or mixed solvent such as dichloroethane.

The epoxy resin (t1) containing a hydroxyl group in the molecule used for producing the urethane-modified epoxy resin (n) is preferably a urethane-modified epoxy resin (n). An epoxy resin having an average of more than 1 substituted or unsubstituted glycidyl ether group in the molecule, having a glycidyl ether number of 100 to 4,000 and having a substituted or unsubstituted glycidyl ether group represented by the formula (where 2 is a hydrogen atom, a methyl group, or an ethyl group) (II-1-1),
Epoxy resin (II-a-2) having an average of more than one substituted or unsubstituted dalicidylesthyl group in the molecule represented by the formula (where 2 is a hydrogen atom, a methyl group, or an ethyl group),
Epoxy resin (I-
a-3) etc. are included.

The epoxy resin (Il-a-1) having one or more substituted or unsubstituted glycidyl ether groups in the molecule is
Examples of such epoxy resins (n-a-1) include epoxy resins obtained by glycidyl etherification of alcoholic hydroxyl groups and nixy resins obtained by glycidyl etherification of phenolic hydroxyl groups. Polyglycidyl ether of polyhydric alcohol (II-a-1-i) Polyglycidyl ether of polyhydric phenol having one or more aromatic nuclei (II-a-1-i)
-a-1-) and polyphenols of alcoholic polyhydroxyl compounds derived by the addition reaction of polyhydric phenols having one or more aromatic nuclei and alkylene oxides having 2 to 4 carbon atoms. Glycidyl ether (na
-1-c) etc.

However, the above polyglycidyl ether (II-a-1-
b), polyglycidyl ether (I-a-1-ent) or polyglycidyl ether cn-a-1-c), for example, polyhydric phenol having at least one aromatic nucleus and epihalohydrin Epoxy resins containing polyglycidyl ether as the main reaction product, such as those obtained by reaction in a conventional manner in the presence of a basic catalyst or a reactive amount of a basic compound such as sodium oxide; A polyhydroxyl compound derived by an addition reaction between an alcohol or a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms and a bihalohydrin such as boron trifluoride. An epoxy resin such as that obtained by reacting a polyhydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of an acidic catalyst amount or at least one aromatic Polyhydric phenol having a group nucleus and shrimp halohydrin are reacted by a conventional method in the presence of a catalytic amount of a basic catalyst such as triethylamine, and a polyhalohyl-P phosphorus ether obtained by reacting with a basic compound such as sodium hydroxide. be able to.

Also, Nixy resin (II-a-2) having an average of 1 more substituted or unsubstituted glycidyl ester groups in the molecule
Also included are epoxy resins such as those obtained by polymerizing glycidyl methacrylate synthesized from shrimp halohydrin and methacrylic acid.

In addition, epoxy resins (I
Examples of I-a-3) include epoxy resins obtained from aromatic amines (e.g. aniline or anilines with alkyl substituents in the nucleus) and shrimp halohydrin, initial charge of aromatic amines and aldehydes (e.g. aniline- Examples include epoxy resins obtained from a formaldehyde initial condensate, an aniline-phenol-formaldehyde initial condensate) and shrimp halohydrin.

In addition, conventionally known epoxy resins such as the various epoxy resins described in "Manufacture and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) may also be used. In either case, if the reaction is carried out at a ratio that leaves unreacted hydroxyl groups or leaves hydroxyl groups in the reaction product (for example, at a ratio of 1 molecule or less of shrimp halohydrin per 1 active hydrogen such as hydrogen of a hydroxyl group), hydroxyl groups (
An epoxy resin containing preferably aliphatic hydroxyl groups is obtained.

Particularly in this case, it is preferable that the average number of hydroxyl groups is 0.3 or more in one molecule.

As the incyanate group-containing compound (II-b), the above-mentioned organic diisocyanates, monoisocyanates such as phenyl isocyanate, and polyisocyanates such as triphenylmethane triisocyanate can also be used. Furthermore, a urethane prepolymer containing an isocyanate group at the end obtained from the above-mentioned polyhydroxyl compound and an organic polyisocyanate can also be used. The polyhydroxyl compound mentioned here includes the above-mentioned polyester polyol, polyether 4-liol, and the like.

Epoxy resin containing hydroxyl groups in the molecule (n-
m) and a compound containing an incyanate group (II-b)
The ratio of hydroxyl groups to isocyanate groups when reacting varies greatly depending on the number of hydroxyl groups contained in one molecule of the epoxy resin (II-1), but
:1 to 1:1 is preferable. This urethane-modified epoxy resin (II) may also be produced in a solvent-free system or in a solution state. The urethane-modified epoxy resin (II) produced in a solvent-free system is used after being dissolved in an organic solvent.

As the solvent mentioned here, all those mentioned in the case of I urethane resin (I) can be used.

Polyurethane resin (I) and urethane-modified epoxy resin (
II) may be produced separately and then mixed, or
After producing polyurethane resin (I), first epoxy resin (n
-1) and then add the isocyanate group-containing compound (n
-b) may be added to cause the epoxy resin (II-a) and the compound containing an isocyanate group (II-b) to react. The viscosity of the composition of the present invention thus obtained is usually about 5,000 to 100,000 cps.

Preurethane resin (I) and urethane-modified epoxy resin (
The ratio with II) can be set arbitrarily, but the preferred weight ratio is (I):(D) = 95-30:5-
70. Particularly preferably, the ratio is 90-50:10-50.

Further, fillers and other additives may be added as necessary.

The resin composition of the present invention thus obtained can be used alone, for example, as an adhesive, but it is preferable to add an isocyanate compound as a curing agent at the time of use, similar to ordinary I-urethane resin adhesives. The amount is (
1 to 20 parts by weight based on the resin solid content of I) and (IN),
In particular, it is 5 to 10 parts by weight.

The isocyanate compound is a compound having an isocyanate group alone or in combination with a hydroxyl group, an amino group, or a xyl group, such as triphenylmethane triisocyanate (trade name "Deamodu").
r RJ ), tris(4-phenylisocyanate)
Thiophosphate (product name: “Deamodur RF”)
J), product name “Coronet) LJ, [Deamod
ur L J, TDI () lylene diisocyanate)
Dimer (trade name “Deamodur TT J”),
TDT trinylethe A/) diisocyanate (product name [Hyx・nDMJ], product name "Coronate AP", xylylene diisocyanate TMP adduct (product name "7")
& Anne) TMP Adduct (Product name [Takenate D1
2ONJ), diphenylmethane diisocyanate, hexamethylene diisocyanate, triphenylmethane diisocyanate, TDI and TMP ()rimethylolpropane) adducts (product name: ``L'' can be selected depending on the available surface time and curing conditions. , but is not particularly limited to the above examples.

〔effect〕

The resin composition of the present invention is produced by reacting an appropriate amount of the hydroxyl groups in the epoxy resin added to the polyurethane resin with a compound containing an isocyanate group, thereby converting this urethane-modified epoxy resin into an adherend or its use. It can be added arbitrarily depending on the conditions, so metals, glass, etc.
It not only has excellent adhesion to a wide range of adherends such as wood, but can also be used in a wide range of fields where durability such as heat resistance and water resistance is required.

Such compositions with excellent adhesiveness, heat resistance, and water resistance are used as adhesives, for example, for adhesion of panels such as the adhesion of vinyl chloride, FRP decorative boards, and plywood, and for adhesion of nonwoven abrasive materials.

〔Example〕

Next, the present invention will be explained in detail with reference to examples.
Unless otherwise specified, "part" and "chi" are based on weight. Furthermore, the present invention is not limited to these.

Synthesis example 1. (Preparation of urethane-modified epoxy resin ■) 100g of Epiclon 4050J (bisphenol type epoxy resin, epoxy equivalent 900/-IFlooo, manufactured by Dainippon Ink & Chemicals) was mixed with methyl ethyl ketone 300.9
After dissolving in the solution, diphenylmethane was reacted for 5 hours to obtain a urethane-modified epoxy resin (2).The end point of the reaction was the point at which the isocyanate content became 0.01 or less. The recorded urethane-modified epoxy compound ■ has a non-volatile content of 2.
6, viscosity 2800 Preparation of composition [A] consisting only of fat) 1.6 Molecular weight 2 consisting of hexanediol and adipic acid
After heating and melting 000 polyester preol 200I at 80°C, 9 g of 1,4-butanediol was added,
Mix evenly. To this was added 49 g of diphenylmethane diisocyanate melted at 50°C, and the mixture was stirred and mixed uniformly to obtain polyurethane resin (2).

This polyurethane resin (50.9) was dissolved in 150 g of methyl ethyl ketone to obtain a composition [A] consisting only of a polyurethane resin.

The obtained composition [A] had a non-volatile content of 25 cm and a viscosity of 4LO.
OOeps (at 25°C).

Synthesis example 3. (Preparation of composition CB consisting of polyurethane resin and epoxy resin) Polyurethane resin ■50.9 was mixed with methyl ethyl ketone 15
After dissolving in 0g, "Epicron 4050" 20.9
and methyl ethyl ketone 601! Add "Epicron 4"
After confirming that 050 J was completely dissolved and became uniform, it was taken out and a composition (B) made from polyurethane resin and epoxy resin was obtained.

The resulting composition CB) had a non-volatile content of 25 cm and a viscosity of 34.5
00Cpl (at 25°C).

Synthesis example 4. (Preparation of composition [C] consisting of polyurethane resin and urethane-modified 4-oxy resin) After dissolving 50 g of polyurethane resin ■ in methyl ether ketone 1509, add 100 g of urethane-modified epoxy resin ■, and check that it becomes uniform. After confirmation, it was taken out to obtain a composition [C] consisting of a polyurethane resin and a urethane-modified epoxy resin.

The resulting composition (C) had a nonvolatile content of 25% and a viscosity of 38*2.
00 cps (at 25°C).

Synthesis example 5. (Preparation of composition CD consisting of polyurethane resin and urethane-modified epoxy resin) Dichloromethane 8
Polyester with a molecular weight of 2000 consisting of 1,6 hexanediol and adipic acid in 00I? Riolu 200g
4.51 was added to 1,4-butanedi- and dissolved uniformly, 37 g of diphenylmethane diisocyanate was added and dissolved uniformly, and diptyltin dilaurate 2 was added.
After adding 0 ppm and reacting at 40° C. for 10 hours, it was confirmed that the isocyanate groups were completely gone. Add "Epicron 1050J (1450pJ5 per epoxy) to this solution"
00, Dainippon Ink & Chemicals Co., Ltd.) was added, and after it was completely dissolved and homogeneous, diphenylmethane diisocyanate 7.2 # was added and the reaction was carried out at 40°C. The end point was when the viscosity became constant. A composition CD) consisting of a polyurethane resin and a urethane-modified epoxy resin was obtained.

The resulting composition to) had a non-volatile content of 32% and a viscosity of 45.0.
00 eps (at 25°C).

Examples 1-2, Comparative Examples 1-2 About the obtained compositions 1. YRS K6852 (compression shear adhesive strength testing method for adhesives).

It was set as 7 days. Heat resistance is 60'CX 24 hrm
,Water resistance is immersed in water at 30℃ for 3 hours, then immersed in water at 20℃ for 10 minutes. All measurements were taken at 20°C.

Both compositions (c) and CD) of the present invention are
It was confirmed that it not only showed high normal strength but also had excellent heat resistance and water resistance.

Example 3, Comparative Example 3 After impregnating a nonwoven fabric with the composition as described below, the rotation speed was
A hardening process was performed. After the treatment, the copper plate was dry ground and evaluated by observing the ground surface.

It has been revealed that the composition of the present invention has excellent heat resistance, so there is no fusion after grinding, and it is also excellent as an adhesive for nonwoven abrasive materials.

Claims (1)

[Claims] From a polyurethane resin (I) and a urethane-modified epoxy resin (II) obtained by reacting an epoxy resin containing a hydroxyl group in the molecule (II-a) and a compound containing an isocyanate group (II-b). A resin composition.