JPS58141250A - Composite material having cured film - Google Patents

Abstract

PURPOSE:To obtain a substrate having improved surface hardness, resistance to wear, chemicals, corrosion and light, etc., by coating a substrate with a mixture contg. a hydrolyzate obtd. by adding an aq. hydrochloric acid soln. to a silicon compd., a hydrolyzate obtd. by adding an aq. hydrochloric acid soln. to an epoxy group-contg. silicon compd. and SnCl2. CONSTITUTION:A substrate is coated with a mixture contg. a hydrolyzate (A) obtd. by adding an aq. hydrochloric acid soln. to an epoxy group-contg. silicon compd. of formulaI(wherein R<1> is an org. group contg. an epoxy group; R<2> is a 1-5C alkyl group; a is 1-3), a hydrolyzate (B) obtd. by adding an aq. hydrochloric acid soln. to a silicon compd. of formula II (wherein R<3> is a 1-6C alkyl, vinyl, methacryloxy, mercapto, a chlorine-contg. org. group; b is 0-3) and SnCl2 (C). The coated substrate is cured. Examples of said substrates are plastics, wooden articles and metallic articles.

Description

[Detailed Description of the Invention] The present invention is applicable to plastic products, wood products, metal products, etc. ! This article relates to composites with cured films that have improved surface hardness, abrasion resistance, chemical resistance, corrosion resistance, light resistance, etc.

For example, plastic molded products, including polycarbonate resin, acrylic resin, styrene resin, and vinyl chloride resin, have excellent transparency, light weight, easy processability, and shock resistance, but they also have excellent abrasion resistance and It has the disadvantage of poor chemical properties and being easily attacked by 4IK solvents.

Although many methods have been proposed to overcome these drawbacks, none of them have been fully satisfactory.

For example, a combination of organoalkoxysilane, tetraflukoxysilane, etc. or l! Mixtures with various resins are known, but they have excellent abrasion resistance, hot water resistance,
Good compactness, adhesion, and pot life after treatment were not obtained. Is the reason behind this the catalyst? The key is in the crosslinking agent.

Catalysts, metals, and crosslinking agents that have been proposed in the past include the following books. That is, hydrochloric acid, nitric acid, sonoic acid, phosphoric acid, formic acid, sulfonic acid, para-toluenesulfonic acid, fluorine trifluoride, and 6 of them.

SnO4, ZnC15, Fe (!ts, uom,
Lewis acids and their complexes such as 8bO#, Ti01s, organic acid metal salts such as sodium formate, zinc naphthenate, tin octylate, perchloric acid, ammonium perchlorate,
Alkali such as ammonium salt, phoride, fluoride, sodium hydroxide, polyhydric carboxylic acids, and organometallic alcoholades such as tetrabutoxytitanium.

Titanyl acetylacetonate, aluminum 7-cetyl gamma tonate-based gold M/cetyl 7-cetonate-based complex of various metal compounds, n-butylamine.

Amines such as guanidine, imidazole, and amino-containing silicon compounds all suffer from various drawbacks. Namely, hydrochloric acid, nitric acid, formic acid, sulfonic acid para-toluene sulfone, alkali 1+1°ZnC/a, F
eOm, htata, 8bOjm, organometallic salts, etc. are not practical because the hardening of the obtained cured film is insufficient, and Ami 7 requires high temperature to cure sufficiently, and the cured film is difficult to cure. In addition, the pot life of the processing solution is extremely long, making it impractical.
Cured films using polyhydric carboxylic acids*, phorides, fluorides, and boron trifluoride have insufficient hot water resistance, and are practical because they avoid the decrease in paper hardness that occurs when immersed in hot water. Tangent metal alcolades are impractical because the pot life of the treatment solution is short, and complexes of metal compounds require higher temperatures than amines to fully cure. The salts such as ammonium perchlorate color the cured film, and the pot life of the treatment solution is short, so it is not practical.
4s The quality of the hard film obtained with the iQ&deta paper seems to be good, but the pot life of the processing solution is short and it is not practical.

The present invention overcomes the above-mentioned drawbacks and! I side ii! It has excellent abrasion resistance, chemical resistance, chemical resistance, and light resistance.The cured film has good adhesion to all liquid types and substrates, and exhibits excellent performance in ib and hot water resistance. , the pot life of the treatment liquid is long (in addition, it is a catalyst that can be cured sufficiently in a relatively low temperature and in a short period of time, and salt is used as a crosslinking agent).
This is a book that found that the combination of C1x is optimal.

In other words, the present invention combines the epoxy group-containing silicon compound represented by the general formula (1) with a hydrochloric acid aqueous solution i1 and the silicon compound contained in the general formula (2) into #A#
Hydrolyze with an aqueous solution and add 9 things and a little Sn Olz? c) It is a sleeve joint made by coating and curing a mixture characterized by containing spiders.

Typical examples of the epoxy group-containing silicon compounds that are attenuated by the general formula (1) are as follows.

FIa-81-(OR”), -I!L(1) (in the formula Bl
is an organic group having an epoxy group, R3 is a carbon number of 1 to 5
β-glycidoxyethyltrimethoxysilane r-glycidoxyprobyltrimethoxysilane bis(glycidoxymethyl)dimethoxysilane tris(glycidoxy)methoxysilane 3.4-
Eboxycyclohexylmethyltrinotoxysilane 3.
These are 4-epoxycyclohexylmethyltriethoxysilanes, including those in which a part or all of the alkoxy groups are replaced with hydroxyl groups and those in which the hydroxyl groups are condensed together by hydrolysis after adding an aqueous hydrochloric acid solution.

It is 4 or less, which is typical of the silicon compound represented by the general formula (2).

R"b -at -(OR"), -1) (R1 in the formula) is an alkyl group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, a mercapto group, or an organic group having chlorine, and b is 0 to
5) ethyltriethoxysilane ethyltriethoxysilane vinyltriethoxysilane r methacryloxyglobil trimethoxysilane mercaptoprobyl trimethoxysilane chloroglobil trimethoxysilane tetramethoxysilane tetraethoxysilane, etc., and aqueous hydrochloric acid solution is added. As a result of hydrolysis, some of the alkoxy groups are replaced with hydroxyl groups, and the hydroxyl groups are condensed together. When used for performing hydrostatic fisting, the cured film tends to become uneven,
In some cases, the cured film turns white.

As mentioned above, the hydrochloric acid aqueous solution acts as a hydrolysis catalyst for alkoxy groups, and it is preferable that the amount of the hydrochloric acid aqueous solution added is 5 to 50 wt- relative to the weight of the silicon compound. Even if the coating is cured, the abrasion resistance of the coating remains.However, by further increasing the amount added or increasing the concentration of hydrochloric acid, the aqueous hydrochloric acid solution becomes a catalyst for the hydrolysis of alkoxy groups and an epoxy group. acts as a ring-opening catalyst, and the quality of the resulting cured film improves rapidly, but the pot life of the treatment solution becomes extremely long.Therefore, while keeping the amount of hydrochloric acid aqueous solution low, adding a small amount to Bn acts as a catalyst and crosslinking agent
Using C1*1. -1, the pot life of the papermaking and processing solution is at risk, and it is also possible to cure the film sufficiently in a short time at a relatively low temperature, and also to have good adhesion to the substrate. An addition amount is α01~5wt1 based on the weight of the epoxy group-containing silicon compound, α01fi
- If the coating is less than 5 vt, the quality such as abrasion resistance and hot water resistance is insufficient, and if it is 5 vt or more, the pot life of the treatment liquid is short.

As mentioned above, Booty differs from other epoxy ring-opening catalysts in that it not only acts as an epoxy WalI catalyst, but also as a crosslinking agent, making the resulting cured film denser, and increasing the density of the cured film. It also contributes to ensuring adhesion to the base material while maintaining hardness, abrasion resistance, and hot water resistance.

Although 1nQb has the same effect as 8nQt*, it tends to shorten the pot life of the treatment solution, and it is also possible to use Booty or Br5O1* ice solution as a catalyst or crosslinking agent instead of using an aqueous hydrochloric acid solution. A cured film formed by a liquid will eventually have inferior wear resistance, and if a maroxy group hydrolysis catalyst other than an aqueous hydrochloric acid solution is used in combination with 8nO1 richness, for example, if a hydrolysis catalyst has a boiling point higher than the firing temperature of the oxide film. The pot life of the treatment liquid is short, many of them color the cured film, and the abrasion resistance of the cured film is one rank better than that of an aqueous hydrochloric acid solution. On the other hand, nitric acid, acetic acid,
When formic acid was used in combination with a volatile hydrolysis catalyst, the abrasion resistance of the cured film was extremely low and could not be obtained.

Solvents that may be included in the treatment liquid of the present invention include methanol,
Alcohols such as ethanol, globanol, impropatol, butanol, imbutanol, methyl cellosolve, ethyl cellosolve, ethers, esters, carboxylic acids, halides, aromatic compounds, ketones, etc. S excerpts or a mixture can be used. Is it even more necessary? Depending on the situation, a surfactant (flow control agent) may be used to further improve the appearance of the cured film.

The coating method is the known dipping method, the blowing method, or the roll coater.
Any law may be used. The conditions for firing the cured film are as follows.
, 10 minutes to 4 hours. The thickness of the cured film varies depending on the purpose, but α1 to 20jm is good.

In addition, the above-mentioned silicon compound and various monomers and polymers listed in the Japanese book may be added to this treatment liquid. or polymers, celluses, or 10% of them based on the weight of the silicon compound.
Used below 0wt.

The essence of the present invention will be explained in detail with reference to Examples below, but the present invention is not limited thereto.

The performance of the cured film was evaluated using the following method.

(Abrasion Resistance) Abraded with $0,000 steel wool, scratch resistance was evaluated as follows.

It is strong and will not get scratched even if the car is worn out.

B1 Strongly worn and has some fecal matter.

Even a weak C0 wear will cause damage.

(Adhesion) The so-called base test shows that the cured film is hardened with a knife! 11iK1■
After applying cellophane tape, peel off the tape and mark the number of squares as the number of squares plus the number of squares.

(Hot water resistance) The condition of the cured film was examined by immersing it in boiling water for 1 hour.

(Heat resistance) After being stored in a drying oven at 150° C. for 100 hours, the state of the cured film was examined.

(ik4 Mulberry quality) Immerse and polish in 5-thiosulfuric acid, 1'l sodium hydroxide, 95% ethanol, acetone, toluene, and IN* salt water at 40°C for 7 days, and examine the condition of the cured film.

(Light resistance) Condition of cured film after 400 hours using 7 edometer test Example 1 100 parts of isopropyl alcohol 88.5 parts of Kr-glycidoxypropyltrimethoxysilane and 57 parts of tetramethoxysilane were dissolved, and Add 7 parts of LO5NO5N dissolved acid aqueous solution, stir at room temperature for 2 hours to perform hydrolysis, add the resulting firefly, 50 parts of 7-cetyl-7-cetone, and ripen at room temperature for more than 20 hours. 4 parts of α and a small amount of a flow control agent were added and stirred to prepare a treatment liquid.

The cleaned AvCP-39 board and the acrylic IEK treatment solution were applied by dipping, the former at 130°C for 90 minutes and the latter at 80°C.
C. for 3 hours. The obtained large cured film has a film thickness of 3'
Both are transparent sand, abrasion resistant chem, adhesion 100/100, hot water resistant, IO heat resistant.

The chemical resistance and light resistance were also good, and the abrasion resistance and adhesion after the hot water resistance test were A1 and 100/100.

Further, # treatment solution □ was left at room temperature, 10 days later, 20 days later, 3
After 0 days and 40 days, it was applied to KOR-59 board and acrylic board, and the quality was 1111! did. The pot life of the treatment solution is long and good, one month.

Example 2 In 100 parts of isopropyl alcohol, 100 parts of 3.4-functional poxycyclohexylmethyltrimethoxysilane and 65 parts of nat-2-ethoxysilane were dissolved, and 495 parts of WKo, 05N hydrochloric acid aqueous solution was added thereto, followed by stirring at room temperature for 2 hours. Aged for more than an hour. The firefly, 0 parts of methanol, 50 parts of inbutanol, 8 parts of C1*α, and a small amount of a flow control agent were added and stirred to prepare a treatment liquid.

Apply the treatment liquid to the cleaning agent 0R-59 plate by dipping method,
It was baked at 0°C for 2H. The obtained cured film has a film thickness of 2.5
Transparent in m m, abrasion resistance is A, adhesion is 100
/100, hot water resistance, heat resistance, chemical resistance.

The light resistance was also good, and the abrasion resistance and adhesion after the hot water resistance test were 100/100.

Also, it was a two-month period of pot life Fi along with Nyori.

Comparison 111 1 part In the preparation of the treatment liquid in Example 1, replace flnojm with α07 parts of ammonium perchlorate, and replace the 4-benzene solution of aluminum acetylacetonate with tS@5j8nO.
Five types of treatment solutions were prepared by adding 0.6 parts of silica to each of the solutions.

The &L treatment solution was applied to washed OR-59 boards and acrylic boards in the same manner as in Example 1, and the quality of the fired bales was checked.

The large cured film obtained using ammonium perchlorine was colored brown and the pot life of the treatment solution was short.

Abrasion resistance FiB of the cured film obtained using aluminum acetylacetonate, and adhesion S to the substrate
It was poor at O/100.

Although the quality of the nine-layer film obtained using SnO was good, the pot life of the treatment solution was short, about one week.

Comparative Example 2 In preparing the treatment liquid in Example 1, instead of 005y hydrochloric acid aqueous solution K, 50 parts of 0.01N nitric acid aqueous solution and 0.01N nitric acid aqueous solution were added.
A treatment solution was prepared using 50 parts of 02NH804 aqueous solution and 25 parts of 8591 formic acid, and KOF was prepared as in Example 1.
-39 plate, acrylic plate coated, fired, and cured film product IF
It was till.

Both 'cured films have abrasion resistance of B and adhesion of 50.
~707,100, which was insufficient. Further, the tomocured film obtained by using an aqueous solution of α0218 was colored brown.

As described above, in the embodiments for station use, glasstics were used as the base material, but the present invention can also be applied to other base materials such as wood and metals.

Applicant Shares as Company Suwa Seikosha Agent Patent Attorney Mogami Written Amendment to Procedures (Voluntary) Commissioner of the Japan Patent Office l Display of the Case Patent Application No. 12190 of 1983 2 Title of Invention Hardening gtw Compound 3, Amendment Part □ - Actor Tsuneya Nakamura 4, Agent F - Continuing amendment (written spontaneously) 1. Details page 10, line 5, ``Even if 1 monomer polymer is added'', there is a meeting ``Various monomers, polymers'' Even if t-addition is made, Vr is corrected.

2. Details Jl 1G member 3rd line from the bottom says ``#00 0 steel wool'', says ``#o o u steel wool JKl?I correct.

5, -a accumulation 15 contribution 2nd line (-LLo 2 NH, "? O, aqueous solution" stop t
luo 2 NH, 8Q4 aqueous IfLft”.

that's all

Claims (1)

[Claims] The following (A), ω) and (0) ((transition) General formula (1) F'h -Si -(OR)
)4-. (In the formula, R1 is an organic group having an epoxy group, R3 is an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 3 carbon atoms.) A hydrochloric acid aqueous solution is added to a silicon compound having at least one kind of epoxy group. hydrolyzate. 03) General formula (2) R”h −st −(o R
”)4-b (in the formula, R3 is an alkyl group having 1 to 6 carbon atoms,
A hydrolyzate obtained by adding an aqueous hydrochloric acid solution to a silicon compound of at least 41s which can be separated by a vinyl group, a methacryloxy group, a mercapto group, or a chlorine-sounding group, and the number is 0 to 5. (C) A composite having a cured film coated with a mixture containing at least Sn ctt .