JPH03160049A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. capable of forming a film excellent in the flexibility, adhesive properties, adhesion between layers, and corrosion resistance by compounding a copolymer of an org. phosphoric ester monomer with an epsilon-caprolactone-modified monomer with a curing agent. CONSTITUTION:The title compsn. is prepd. by compounding: a copolymer obtd. by copolymerizing a monomer mixture contg. a reactive polar monomer component comprising an org. phosphoric ester monomer and an epsilon-caprolactone- modified monomer of the formula (wherein R1 is H or methyl; and X>=1) consisting of a hydroxylated monomer partially or totally modified with epsilon- caprolactone, or pref. a copolymer obtd. by copolymerizing 0.01-5wt.% org. phosphoric ester monomer, 10-16wt.% epsilon-caprolactone-modified monomer, and 89.99-35wt.% monomer copolymerizable with the foregoing two monomers; with a curing agent pref. comprising a melamine resin or a polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition. More specifically, the present invention provides a particularly flexible copolymer containing a specific copolymer based on organic phosphate group-containing monomers and ε-caprolactone-modified monomers, and a curing agent. ,
The present invention relates to a resin composition that forms a film with excellent adhesion, interlayer adhesion, and corrosion resistance.

The resin assembly of the present invention is particularly useful for paints, adhesives, or sealants, and especially as a vehicle for hardening type high solids paints.

[Conventional technology]

In the paint field, efforts are being made to reduce the amount of solvents used and the amount of volatile matter released into the atmosphere, and the trend is to shift to high solids, which is steadily progressing toward realization. .

In order to achieve such a high solubility, it is necessary to make the coating resin itself low in molecular weight and at the same time to improve its solubility in solvents.

By the way, regarding the improvement of solubility due to the structure of resin, for the purpose of lowering the glass transition temperature, it is possible to improve dissolution by blending polyester or alkyd resin, or by adjusting the concentration of hydroxyl groups and carboxyl groups. It is intended to improve sex.

In this way, the desired improvement in solubility can be achieved, but on the other hand, there is a significant decrease in adhesion to the substrate and corrosion resistance due to the decrease in the polarity of the resin. Another drawback is that the flexibility is extremely reduced as the molecular weight is lowered.

Taking into consideration the existence of these various drawbacks, a method was developed in which ε-caprolactone was added to the hydroxyl group in the acrylic resin, as described in U.S. Pat. No. 4,546,046. In fact, as the modification rate of lactone is increased, although the flexibility itself is increased, there is an extreme decrease in adhesion and interlayer adhesion.

Under these circumstances, in order to improve such adhesion, a method of copolymerizing so-called polar heptanomers has been widely adopted, but most of these methods are based on polymers with short side chains such as acrylic acid and itaconic acid. What if it uses a polar heptamer? The reality is that the solubility has deteriorated significantly, and therefore no definitive solution has been found at present.

[Problem to be solved by the invention]

However, in view of the various drawbacks of the prior art as described above, the present inventors have developed a resin that can improve properties such as flexibility and adhesion without reducing solubility in solvents. In search of this, he began earnest research.

Therefore, the problem to be solved by the present invention is to provide a vehicle that is particularly useful as a vehicle for curable high solids paints, which has significantly improved flexibility, adhesion, and corrosion resistance, and which also has an 8g solvent content. It is an object of the present invention to provide a practical resin composite sole that does not leave any problems in terms of solubility.

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
A resin composition containing a curing agent and a specific copolymer used in combination with an organophosphate group-containing monomer and an ε-caprolactone-modified monomer has a low solubility in an organic solvent. In particular, resin compositions capable of forming films with excellent flexibility, adhesion, interlayer adhesion, and corrosion resistance, particularly resin compositions for paints, and more preferably resin compositions for high solid paints. By discovering this, the present invention has been completed.

That is, the present invention provides organic phosphate group-containing carmers (
a-1) and some or all of the hydroxyl group-containing monomers are ε-
In a form modified with caprolactone, a monomer represented by the general formula... The copolymer (A) obtained by
) in a form in which part or all of the hydroxyl group-containing monomer is modified with ε-caprolactone, represented by the general formula... (1). 10 to 60% by weight of ait form M(a-2)
and 89.99 to 3 of the vinyl monomer (a-3) copolymerizable with the above monomers, l(a-1) and (a-2).
A copolymer obtained by copolymerizing with 500%, more preferably a low molecular weight copolymer (A) having a glass transition temperature of 30° C. or less and a number average molecular weight of 5,000 or less; A curing agent (B), preferably a melamine resin or a polyisocyanate compound, more preferably a melamine resin etherified with a C1 to C4 monohydric alcohol, or a polyisocyanate compound. This is what we are trying to provide.

Here, first of all, only particularly representative monomers (a-1) used in preparing the above-mentioned copolymer (A) are listed. Is the degree of polymerization of [2-(meth)acryloyloxyethyl] acidophosphate and polyethylene glycol 1 to 6? Mono [2-(meth)acryloyloxypolyethylene glycol] acid phosphate, mono[2-(meth)acryloyloxypolyethylene glycol] acid phosphate in which the degree of polymerization of polypropylene glycol is 1 to 6, or C to C1
(2) Di[2-(meth)acryloyloxyalkyl]acid phosphates having an alkyl group or further esterified with a benzyl group.

And the organic phosphate group-containing monomer (a-1)
The amount used is within the range of 0.01 to 5% by weight.
Preferably, a range of 0.1 to 2% by weight is appropriate.

If it is less than 0.01% by weight, characteristic effects such as adhesion and corrosion resistance cannot be expected to occur, while if it exceeds 5% by weight, the resultant copolymer will inevitably be susceptible to organic solvents. Either case is undesirable because the solubility tends to be extremely reduced, which may cause problems in, for example, the design of high solid content paints.

In addition, each of the following monomers (a-2) to be copolymerized with the monomer (a-1), furthermore, the monomer (
As for the usage amount of a-3), the former (a-2) is 10
-60% by weight, preferably 15-50% by weight, the latter (a-3) being 89.99-35% by weight,
Preferably, it is within the range of 84.9 to 45% by weight.

Next, the so-called ε-caprolactone-modified monomer (hereinafter abbreviated as lactone-modified monomer), which is a form in which part or all of the hydroxyl group-containing monomer described above is modified with ε-caprolactone, is Monomers represented by the general formula (1), which are obtained by adding 1 mol or more, preferably 1 to 6 mol, of ε-caprolactone to a hydroxyl group-containing monomer as described below, Usually, it refers to a mixture of adducts with respective molar numbers, and among them, to exemplify only the most representative ones, "Plaxel FM or FA series" manufactured by Daicel Chemical Industries, Ltd. ” etc.

As the hydroxyl group-containing monomer used to prepare such a lactone-modified monomer, any known and commonly used monomers can be used, but only the most representative ones are listed below. - (meth)acrylates such as hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate or 2,3-dihydroxybutyl (meth)acrylate; hydroxyethyl vinyl ether or vinyl ethers such as hydroxybutyl vinyl ether; or allyl alcohols or allyl compounds such as hydroxyethyl allyl ether.

The amount of the hydroxyl group-containing monomer used is preferably within the range of 80 to 200 in terms of hydroxyl value.

If it is less than 80, it will be difficult to obtain a sufficiently cured coating film, while if it is more than 200,
Either case is unfavorable because the solvent solubility of the resulting copolymer inevitably decreases.

The amount of lactone-modified monomer itself used in the hydroxyl group-containing monomer is 1/100n at most.
Mol% is preferred. When n=2 or more and as n increases, by adjusting the proportion of the lactone-modified monomer as described above, deterioration in adhesion to materials, glabellar adhesion, etc. can be avoided.

That is, the maximum amount is 50 mol% when n = 2, 25 mol% when n = 4, and 1/6 mol% when n = 6. This is the range of the amount of ε-caprolactone added to the hydroxyl group-containing monomer when preparing the monomer. Furthermore, vinyl monomers (a-3 )
As long as it has copolymerizability, any one can be used, but among them, only representative ones are exemplified: alkyl (meth)acrylates such as Cl to CtZ; Aromatic vinyl monomers such as styrene, α-methylstyrene, t-butylstyrene or vinyltoluene; 2-ethoxyethyl (meth)
Acrylate, cyclohexyl (meth)acrylate,
Glycidyl (meth)acrylate; (meth)acrylonitrile; 7- or diesters of maleic acid or fumaric acid and 01 to C monohydric alcohols; N
- (meth)acrylamides such as alkoxymethyl (meth)acrylamide. N,N-dialkylaminoalkyl (meth)acrylates: or fluorine-containing vinyl monomers such as tetrafluoroethylene or hexafluoropropylene, or vinyl acetate. Also, (meth)acrylic acid, crotonic acid, itaconic acid,
Unsaturated carboxylic acids such as maleic acid or fumaric acid can also be used. In order to carry out a copolymerization reaction using each of the monomers listed above, known and commonly used polymerization methods can be applied.
Among these, radical solution polymerization is preferable. In particular, to prepare low molecular weight copolymers, mercabutan compounds such as mercabutethanol, thioglycerol or laurylmercabutane; or 2.4
The reaction may be carried out in the presence of a known and commonly used chain transfer agent such as -diphenyl-4-methyl-l-pentene or methyl methacrylate dimer, at a high temperature of 140 to 180°C, or at a low monomer concentration. , whereby the desired copolymer (A) can be easily obtained.

In the case of the radical solution polymerization described above, the solvents include xylene, "Solbefuso" (an aromatic hydrocarbon solvent manufactured by Exxon, USA), n-butanol,
Those commonly used in the preparation of vinyl (co)polymers, such as isobutanol, ethyl acetate, butyl acetate, methyl ethyl ketone, or methyl alkene, can be used as is. In addition, as a radical polymerization initiator, penzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, acetyl hexane, t-butyl peroxybenzoate, t-butyl peroxy-
2-ethylhexanoate, t-amylperoxy-2
- various peroxides such as ethylhexanoate or t-amyl peroxybenzoate; or various azo compounds such as azopisisobutyronitrile or azobis(2-methylbrobionitrile); Those used in the preparation of the co)polymers are used as such.

Furthermore, ionic polymerization such as anionic polymerization and cationic polymerization can also be easily carried out by temporarily protecting the reactive polar group, so such ionic polymerization methods may also be used as appropriate. The copolymer (A) obtained in this way is as follows:
has a glass transition temperature of 30°C or less, and s. ooooo
Those with a number average molecular weight of the following, preferably 1. 00
It is particularly desirable to use those having a number average molecular weight within the range of 0 to 3,000.

In the case of copolymers with glass transition temperatures exceeding 30°C,
Inevitably, the solubility in solvents tends to be insufficient,
Thus, for example, it is no longer possible to prepare high solids paints, and s. In the case of copolymers exceeding ooo, such solubility is also extremely reduced, and therefore
Either of these is undesirable since the purpose of the present invention cannot be achieved. On the other hand, as the curing agent (B), it is desirable to use melamine resin, and furthermore, polyisocyanate compounds and the like can be used.

Among these, it is desirable to use alkylated melamine/formaldehyde resin as the melamine resin.

Such alkylated melamine formaldehyde resin is
Generally, it has an alkyl group of 01 to C0, and is a conventional method in which a monohydric alcohol such as methanol, ethanol, n-probanol, isopropanol, n-butanol or isobutanol is reacted with melamine/formaldehyde resin. It is a melamine resin etherified with a monohydric alcohol. The melamine resin can be used in either monomeric or polymeric form. Preferably, hexamethoxymelane is
300J (Mitsui Cyanamid Co., Ltd. product) is
This is a typical commercial product. Other useful resins are methoxy/butoxy methylmelane.

In addition, to mention only particularly representative polyisocyanate compounds, diisocyanates such as tolylene diisocyanate or hexamethylene diisocyanate; Adducts with alcohols; or products with free isocyanate groups that are reactive towards active hydrogen, such as reaction products of 1 mole of water and 3 moles of the diisocyanates listed above. , r h/
7ku DN-950 is also L<Ha D-750 JC Dainippon Ink & Chemicals Co., Ltd. product] or "Desmodule N"
J (product of Bayer AG, West Germany) is a typical commercially available product.

As for the usage ratio of the copolymer (A) and the curing agent (B), first, in the case of a melamine resin curing agent, (A)
:(B) weight ratio is within the range of 40:60 to 85:15, preferably 60:40 to 80:2
In the case of a polyisocyanate compound curing agent, the hydroxyl group in (A) and the (B)
The equivalent ratio with the isocyanate group in the isocyanate group is 1.2:0.8
A range of 0.8=1.2, preferably 1:1 is appropriate.

〔Effect of the invention〕

In this way, copolymer (A) precipitate (A) and curing agent (8
The PJl resin composition of the present invention, which mainly contains the component The cured coating film obtained using a material has flexibility,
It has excellent adhesion to metal materials, corrosion resistance, and glabellar adhesion, and for this reason, the resin composition of the present invention can be used for line painting of light electrical equipment, steel furniture, or building materials, etc. It can be used in a wide range of fields, including tosop coat for automobiles, adhesives, and sealants.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 [Example of Preparation of Copolymer (A)] 300 parts of xylene and 40 parts of n-butanol were placed in a 4-volume flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a dropping funnel.
After the temperature was raised to 130° C. while introducing nitrogen gas, a raw material mixture as shown below was added dropwise at a constant rate over 8 hours using a dropping funnel.

Styrene 250 parts 2-Hydroxyethyl methacrylate 200/l "Plaxel FA-IJ (above) 130 ethyl acrylate 200 methyl acrylate 2IO Mercabutoethanol 40 xylene 38 Even after the dropping is complete,
The reaction was continued by maintaining the same temperature for 30 minutes, and t
-butylperoxy-2-ethylhexanoate 10
1 part was added thereto, and the reaction was continued by maintaining the same temperature for an additional 3 hours to obtain a solution of the desired copolymer (A). Hereinafter, this will be abbreviated as copolymer (A-1), and its characteristic values are shown in Table 1.

Reference Example 2 (same as above) A solution of copolymer (A-2) was obtained in the same manner as Reference Example 1, except that the composition of the raw material mixture to be added was changed as follows.

Styrene 350 parts Methyl methacrylate 60 Plaxel FA-2J (mentioned above) 200 2-hydroxyethyl acrylate, 160 n-butyl acrylate 200 -Azobisisobutyronitrile 50 Thioglycerol
30 The characteristic values of this copolymer and copolymer solution are shown in Table 1.

Reference Example 3 (Same as above) In a reaction container similar to Reference Example 1, "Solbetsuso LOOJ" was added.
After charging 220 parts of the above-mentioned product) and raising the temperature to 150° C. while introducing nitrogen gas, a raw material mixture having the following composition was added dropwise at a constant rate over 6 hours using a dropping funnel.

styrene. 250 parts ethyl acrylate} 110〃2
-Hydroxyethyl methacrylate 180〃"Plaxel FA-4J (mentioned above) 360〃
"Hosmer PPJ (previous company product) 40 methacrylic acid 10 n-butyl acrylate 50 #Sec-phenylethyl alcohol 50 30 minutes after the completion of dropping,
lO of t-amyl baroxy-2-ethylhexanoate
and 50 parts of "Solvesso 100" were added dropwise at a constant speed for 30 minutes, and the reaction was continued by maintaining the same temperature for an additional 4 hours to obtain a solution of the desired copolymer (A). .

Characteristic values for the copolymer and its solution are shown in Table 1.

Reference Example 4 (Same as above) A solution of the desired copolymer (A) was obtained in the same manner as Reference Example 3, except that a raw material mixture having the composition shown below was used.

Styrene 100 parts n-butyl methacrylate 150 lauryl methacrylate 200 "Plaxel F
The characteristic values of the A-IJ 500 hexanoate mercabutoethanol 50 copolymer and its solution are shown in Table 1.

Reference Example 5 (same as above) In a reaction vessel similar to Reference Example 1, “Solvesso 100 J
Prepare 300 parts of and 112 parts of petyl cellosolve,
While introducing nitrogen gas, the temperature was raised to 135° C., and a raw material mixture as shown below was added dropwise using a dropping funnel over a period of 5 hours.

Styrene 200 parts 2-ethylhexyl methacrylate 300 4-hydroxybutyl acrylate 150 "Plaxel FA-I"
J 120# “Plaxel FM-I
J (supra) 150 After the completion of the dropwise addition, the temperature was kept at the same temperature for 5 hours to obtain a solution of the desired copolymer (A). The characteristic values of this product are shown in Table 1.

Reference Example 6 (Preparation agent for control copolymer) A control copolymer (A' -2) solution was obtained.

Styrene 350 parts 2-hydroxyethyl acrylate 220 Methyl methacrylate 80 "Hosmer PEJ
30〃n-butyl acrylate
320 Azobisisobutyronitrile
50 Thioglycerol
The characteristic values for the 30 copolymer and its solution are shown in Table 1.

Reference Example 7 (same as above) A control copolymer (A'-
A solution of 2) was obtained. Styrene 350 parts Methyl methacrylate 70 "Plaxel FA-2J 200-
2-hydroxyethyl acrylate 150-acrylic acid 30 n-butyl acrylate 200 azobisisobutyronitrile 50 thioglycerol
30〃The characteristic value for this thing is the first
As shown in the table. Reference Example 8 (same as above) A solution of a control copolymer (A'-3) was obtained in the same manner as Reference Example 2, except that the raw material mixture of Kumikai as shown below was changed. Ta. styrene
350 parts methyl methacrylate
80〃2-hydroxyethyl acrylate 220〃n-butyl acrylate
320 //acrylic acid
30〃Azobisisobutyronitrile 50
l Thioglycerol 30 The characteristic values of this product are shown in Table 1. Examples 1 to 5 and Comparative Examples 1 to 3 Using the respective copolymers obtained in Reference Examples 1 to 8,
Various resin composites were obtained according to the blending ratios shown in Table 2. Next, each of the resin compositions, which are the clear paints obtained in this way, was treated with Ford Cap No.
．． 4 to give 30 seconds. The non-volatile content at that point was measured and shown in the table as "paint non-volatile content".

Afterwards, apply each clear paint to a thickness of 0.6
The coating was applied to a Bonderai l-#144 treated steel plate (mm) by air spraying to a dry film thickness of 30 to 35 μm, and then baked at 160° C. for 20 minutes. Various performances of each cured coating film were evaluated in the manner described below. The results are shown in the same table.

Gloss: Murakami gloss meter (60° specular reflection) Hardness: Pencil hardness Erichsen;
Shock resistance: Tested at 500g using a DuPont tester Adhesion: After cutting into squares (10 x 10), peel off the cellophane tape and write the number of remaining areas (number of remaining squares) Corrosion resistance: After 240 hours of salt spraying at 35°C,
Peel it off with a cellophane table, measure its width, and
Glabella adhesion: Painted with each paint and baked at 170℃ for 20 minutes, 1 hour later, repainted with the same paint and baked at 150℃ for 20 minutes.
x 10), peel off the cellophane tape, and display the number of remaining goblets Solvent resistance: Using gauze soaked in xylene, load 1.5
Judgment of purpose based on the condition of the coating film after rubbing 10 times with kg.Reference example 9 [Preparation example of copolymer (A)] Instead of n-hebutane, use the same amount of methyl amyl ketone. Same as Reference Example 1 except for the changes,
A solution of the desired copolymer (A) was obtained. Hereinafter, this will be abbreviated as copolymer (A-9), and the characteristic values of this copolymer and copolymer solution are as follows.

Non-volatile content: 70% Gardner viscosity at 25°C: L Hydroxyl value: 118 Glass transition temperature: 3.8°C Number average molecular weight:
...1,700 Examples 6 and 7 Using the copolymer (A-9) obtained in Reference Example 9, various resin compositions were obtained according to the blending ratios shown in Table 3. .

Next, various resins, which are the clear paint thus obtained, were mixed with Ford Kafubu No. 1 using methyl amyl ketone. 4 to give 30 seconds. The non-volatile content at that point was measured and shown in the same table as the "coating non-volatile content".

Thereafter, the same procedure as Examples 1 to 5 and Comparative Examples 1 to 3 was carried out, except that the baking conditions were changed to 60°C for 40 minutes.
A cured coating film was obtained, and then various performances of the coating film were evaluated. The results are shown in Table G.

/ / / / / / As is clear from Tables 2 and 3, the resin composition of the present invention has excellent corrosion resistance, interlayer adhesion, and substrate adhesion, and can be used, for example, as a paint. In this case, the non-volatile content of the coating can be significantly increased, resulting in an exceptionally high solids coating.

Claims (1)

[Scope of Claims] 1. Organic phosphate group-containing monomers (a-1) and a form in which part or all of the hydroxyl group-containing monomer is modified with ε-caprolactone, with the general formula ▲ mathematical formula, chemical formula , tables, etc.▼... [I] [However, R_1 in the formula shall represent a hydrogen atom or a methyl group, and x shall be an integer of 1 or more. ] A copolymer (A) obtained by copolymerizing a monomer mixture containing the monomers (a-2) shown as an essential reactive polar group-containing monomer component, and a curing agent ( B) A resin composition comprising: 2. 0.01 to 5% by weight of vinyl monomers (a-1) containing one or more organic phosphoric acid ester groups in one molecule;
There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼...[I] [However, formula R_1 therein shall represent a hydrogen atom or a methyl group, and x shall be an integer from 1 to 6. ] 10 to 60% by weight of monomers (a-2) represented by
A copolymer obtained by copolymerizing the above monomers (a-1) and (a-2) with 89.99 to 35% by weight of the copolymerizable vinyl monomer (a-3). A resin composition comprising (A) and a curing agent (B). 3. 0.01 to 5% by weight of vinyl monomers (a-1) containing one or more organic phosphoric acid ester groups in one molecule;
There are general formulas▲mathematical formulas, chemical formulas, tables, etc.▼...[I] [However, formula R_1 therein shall represent a hydrogen atom or a methyl group, and x shall be an integer from 1 to 6. ] 10 to 60% by weight of monomers (a-2) represented by
Glass transition obtained by copolymerizing the above monomers (a-1) and (a-2) with 89.99 to 35% by weight of the copolymerizable vinyl monomer (a-3). temperature is 30℃
A resin composition comprising: a copolymer (A) having a number average molecular weight of 5,000 or less; and a curing agent (B). 4. The resin composition according to claim 1, 2 or 3, wherein the curing agent (B) is a melamine resin etherified with a monohydric alcohol having 1 to 4 carbon atoms. 5. The resin composition according to claim 1, wherein the curing agent (B) is a polyisocyanate compound.