JPS5930673B2 - Manufacturing method of surface-treated inorganic board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a surface-treated inorganic board.

Inorganic boards that use cement or gypsum as a binder, such as asbestos slate boards, bulk cement boards, and gypsum boards, have excellent fireproofing performance as inorganic materials, and the production volume is increasing year by year as noncombustible materials. With the rapid increase in demand, pre-coated inorganic boards coated with thermosetting paint are attracting attention as building materials.

The reason for this is that the base material itself has excellent fire retardant properties, durable heat insulating properties, and the surface coating has excellent water resistance, weather resistance, and chemical resistance.These precoated boards are suitable for interior use or For use as exterior materials, solid glass finish and ricin finish are the mainstream. However, the currently used pre-coated thermosetting paints do not have sufficient weather resistance or solvent resistance, and when used for prefabricated houses, they must be bonded to surface-treated boards and wood. Most of the adhesives used in this case are pressurized and heated types, so if you are trying to remove adhesive that has stuck to an area other than the required adhesive area, it is necessary to remove the adhesive from the paint film. It has the disadvantages of peeling, discoloration, and staining. The present inventor has completed the present invention as a result of various studies on the manufacturing method of surface-treated inorganic boards with the aim of improving these drawbacks.

That is, the gist of the present invention is (1) a compound having the following structural formula (4) having two (meth)acryloyl groups in one molecule;
) to (self) alone or as a mixture of 10 to 10.
99 weight? and (Ii) (meth)acrylic esters,
Other vinyl monomers 0-50 weight? (IIl) Thermoplastic polymer 0-50 weight? The present invention provides a method for producing a surface-treated inorganic board, which comprises applying a composition comprising the following to an inorganic board, and then curing the composition by irradiating it with ionizing radiation.

The resin having two (meth)acryloyl groups in one molecule used in the present invention has the following structural formulas (4) to (self).

Here, R and Rl are H or CH3 R2 is a C2-10 divalent hydrocarbon (aliphatic, alicyclic)
The polyalkylene glycol residue R3 having 1 to 10 ether bonds in the residue or molecule has two C1 to 20 hydrocarbon residues (aliphatic/aromatic, alicyclic) R4, R5,
R6, R7, Rl2, Rl3 are H or C1-8 substitutions,
Song substituted alkyl group, allyl group, cycloalkyl group R89
R99RlO9Rll9Rl49Rl59Rl69Rl
7 is H or C, ~8 alkyl group, allyl group, cycloalkyl group Rl8 is a C3 or more linear or branched alkyl group, or an acyl group having a C3 or more linear or branched alkyl group P I Rl , is +CH→τ and the alkylene group R2O is C
1 to 10 divalent hydrocarbon residues (aliphatic, aromatic) R2
l is H or lower alkyl group R22 is C1~].

Acid anhydride residues (aliphatic, aromatic, alicyclic)
n is an integer from 0 to 14 LI9m
l9O9PriQ9r9s9t is an integer of Oゝ5 u is O or 1V is an integer of 1 to 20 w is an integer of O to 20 Specific examples of these are as follows.

(4) A reaction product of a polyester resin having a hydroxyl value of 100 to 600 and a substance selected from (meth)acrylic acid, a halide of (meth)acrylic acid, and (meth)acrylic anhydride, such as phthalic anhydride. and acrylic acid condensate of polyester from ethylene glycol (R, Rl
-H,R2-CH2-CH2-R3=-[][)methacrylic acid condensate of polyester from phthalic anhydride and neopentyl glycol (R,Rl2CH3R2=CH
2-J bH2-R3=α).

(B) A reaction product of a monoester diol and a substance selected from (meth)acrylic acid, a halide of (meth)acrylic acid, and (meth)acrylic anhydride, such as R4
, R5, R6, R7 are -CH3 groups and R9Rl9R89R
99RlO9Rll is H, M9l9P is 1,k,0,
q(O acryloxyvalyl acryloxybivalate,
R, Rl, R4, R5, R6, R7 are -CH3 groups, R8
, R9, RlO, Rll are H, m, l, p are 1. k,0
, q is O, methacryloxybivalyl methacryloxybivalate, R, Rl, R4 ~ R, l is H, 1, p is 1k, q is 2m; o is O, 4-acryloxybutyl 4 - Acryloxybutyrate and the like.

C) Reaction products of glycols and (meth)acrylic acid selected from halides of (meth)acrylic acid and anhydrides of (meth)acrylic acid, such as neopentyl glycol diacrylate (R9Rl:HjRl4! Rl
59Rl69Rl7:HraRl2Rl2, Rl=CH3
S21. r, t=0) 1,4-butanediol dimethacrylate (R, Rl=CH3, Rl49Rl5yRl6
9Rl79Rl2tRl3, HriS9t=1, r=O)
etc. )) Monoglycidyl ester or monoglycidyl niter and α. β-monoethylenically unsaturated carboxylic acid or α. A reaction product obtained by reacting an organic diisocyanate with an addition reaction product with a β-monoethylenically unsaturated alcohol, and a 2.4 toluene diisocyanate modified product (R, 8
=C5-C8 acyl group, u=0R1=H. R2O=[
2) A product obtained by reacting hexamethylene diisocyanate with the addition reaction product of butyl glycidyl ether and methacrylic acid (Rl6=n-C4H,-,, u=0, R20=
+CH2+6R1=CH3), etc.

・l) α. A reaction product of β-monoethylenically unsaturated alcohol and acid anhydride is further reacted with α,β-monoethylenically unsaturated glycidyl ester, for example, 2-
Acryloxyethyl 3-acryloxy-2-hydroxypropyl phthalate (R, Rl=H, Rl, =CH2-
CH2-, R22=(011,X=H) 2-acryloxyethyl 3-methacroxy-1-2-hydroxypropyl maleate (R.
2-CH2-, R22=-CH=CH-), and the like. (F) An acid anhydride is added to a polyester resin having a hydroxyl value of 100 to 600, and then α. It is an addition reaction product of β-monoethylenically unsaturated monoglycidyl ester, for example, a polyester made of phthalic anhydride and ethylene glycol to which succinic anhydride and glycidyl methacrylate are added (R, Rl=CH3X-
H, R22=CH2-CH2-R2=CH2-CH2-
, R3=[][) Polyester made from adipic acid and neopentyl glycol to which phthalic anhydride glycidyl acrylate is added (R, Rl, R3=+CH2→
)) etc.

(G bisphenol A-type epoxy resin with (meth)acrylic acid added, for example, Epicoat +828
(manufactured by Ciel Chemical) with acrylic acid added (R,
Rl, X=H, R25=-o-{}-←ba')-0-,
w-0), etc.

En Bisphenol A type epoxy resin with acid anhydride and α
．． A product made by reacting a half ester with β-monoethylenically unsaturated alcohol, such as Epicote◆8
28 with a half ester obtained by reacting phthalic anhydride and 2hydroxyethyl acrylate (R
, RlR25=-0{>- and {>-0-, X=H).

These resins having two (meth)acryloyl groups in the molecule can be used alone or in an appropriate mixture.

Although it is possible to use these resins alone in the composition of the present invention, in order to control the viscosity and improve coating workability, it is also possible to freely adjust the performance of the final coating film, such as hardness and workability. (meth)acrylic acid esters to change or make it easier for the resin to penetrate into the base material.
0 to 50 weight of other vinyl monomers? use

Specific examples of these vinyl monomers include alkyl esters of (meth)acrylic acid represented by the following general formulas, ie, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate (where R26=H or CH
3, R27=C1-18 linear or branched alkyl group) amyl methacrylate, methyl acrylate, engineered methyl methacrylate, isobutyl acrylate, stearyl methacrylate, and the like.

In addition to these alkyl esters, monomers having one or more functional groups which are compatible therewith can also be used. These monomers have the following general formula. Here, R2, is H, -CH3, and H3O is -0H, NH2, N
HR31,NHCH20R3,,0CH20HR31(
CH2O)3, C(CH2O)4NHR31NH, R28 is H, COOR31COO
Represents a group selected from H, CONHR3l, R3l is C
, ~12 alkyl groups X are Cl, Br, F, x=1-4
Some examples indicate integers such as N
-Butoxymethylacrylamide, diethylene glycol diacrylate, 2-H:30xyethyl acrylate, 2-cyanoethyl acrylate, acrylic acid, diacetone acrylamide, 2-acryloxyethylhydroline maleate, 2-acryloxyethyl hydrogen phthalate, 2- Examples include cyanoethyl hydrogen phthalate, N-isopropylacrylamide, and 2-hydroxypropylacrylate, which are not included in the general formula (C) shown above.

Glyceryl trimethacrylate, polyethylene glycol (200) diacrylate, tetraethylene glycol, diacrylate, trimethylol, ethane trimethacrylate, trimethylolpropane triacrylate, and the like are also used. In addition to the above acrylic monomers, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, and monovinyl aromatic compounds such as styrene and α-methylstyrene may also be used. etc. may be used in combination.

These monomers may be used alone or as a mixture of two or more.

In the composition of the present invention, coating workability, pigment dispersibility,
Furthermore, in order to improve the coating performance, it is preferable to use a small amount of a thermoplastic polymer having a high molecular weight, particularly a thermoplastic polymer having a molecular weight of 20,000 or more, as an extender in an amount of 1 to 50% by weight. Preferably 2 to 30 weight? is appropriate. Examples of these thermoplastic polymers include cellulose butyrate acetate. To practice the invention, these compositions may be coated onto an inorganic board and then cured by irradiation with ionizing radiation, where "irradiation" refers to high energy radiation and/or means to impart secondary energy resulting from conversion into x-rays or gamma-rays having an electron or other particle energy of 10,000 electron volts; for this purpose, x-rays,
Although various types of radiation such as gamma rays and beta rays are used, radiation from accelerated high-energy electrons is advantageous both economically and in use, and particularly satisfactory results can be obtained in the present invention. .

There are no particular restrictions on the generation and use of irradiation energy rays, the type of equipment, etc., as long as the ionizing radiation is 100,000 electron volts or more, and there is no particular upper limit on the upper limit, but when carrying out the present invention, 2. There is no need to use more than 10 million electron volts, and 300,000 to 500,000 electron volts obtained by a normal electron beam accelerator can sufficiently achieve the purpose. The characteristics of the inorganic board surface processing method using the ionizing radiation irradiation method of the present invention are that (a) the curing speed of the surface coating film is extremely fast and surface-treated inorganic boards can be mass-produced in a short time;

(b) Compared to conventional heat drying, the equipment area is smaller;
Moreover, the process can be started and stopped in a short time. (c) It is a solvent-free paint that can easily create a thick coating in one coat and does not contain solvents that are not constituents of the coating like conventional thermosetting paints, and does not cause pollution. is extremely rare.

(d) By using the composition used in the present invention as a film-forming material and using ionizing radiation as a curing energy source, the resulting coating film can be completely cured and have a high crosslinking density. The chemical resistance, solvent resistance, weather resistance, etc. of the membrane are superior to those made by conventional methods, and the blocking properties are especially excellent compared to those made by conventional methods. That is what we are doing.

(e) When the composition used in the present invention is applied to an inorganic board, a part of the composition penetrates into the base material, so when such an inorganic board is irradiated with ionizing radiation, it penetrates into the inorganic board. Since the composition can be completely cured, the adhesion between the base material and the surface treatment coating is extremely good.

etc. When carrying out the present invention, it is recommended that the surface coating of the inorganic board be cured at an irradiation dose of 0.2 to 20 mecarats.

Note that it is desirable that the irradiation of ionizing radiation be performed in an atmosphere of an inert gas such as nitrogen gas or combustion gas.

To apply the composition used in the present invention onto an inorganic board, conventional methods such as brushing, roll coating,
This may be done using a normal coating method such as curtain flow coating or spray coating method. The thickness of the surface-treated inorganic pod obtained by the present invention is preferably about 20 to 300 microns.

When carrying out the present invention, a product can be made by applying a single coat and once irradiating with ionizing radiation in the method of finishing the surface treatment coating film, especially solid glass, but depending on the type of composition used, Depending on the type, uneven coating may occur due to the penetration of the composition after application.For this reason, it is necessary to form a uniform coating surface, that is, one that is uniform in terms of film thickness, gloss, and other film performance. In such cases, the composition is first applied to the base material as an undercoat and allowed to penetrate, and then irradiated with 0.2 to 5 mecarats of ionizing radiation to cure and coat the base material surface. After hardening to some extent, the composition is applied as a top coat, and then cured by irradiation with 0.2 to 20 mecarat ionizing radiation, a uniform coated surface can be obtained. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way, and various modifications are possible. All parts in the examples indicate parts by weight. Example 1 Preparation of a resin having two (meth)acryloyl group structures in the molecule In a reaction vessel equipped with a stirrer, thermometer, dephlegmator and nitrogen gas inlet tube, 20,740 parts of phthalic anhydride,
32,080 parts of neopentyl glycol was charged, and the reaction was continued at 210° C. for 5 hours while removing condensed water while blowing nitrogen gas, and the reaction was terminated when the acid value of the reaction solution reached 0.5.

The obtained polyester had a hydroxyl value of 376. 41,780 parts of this polyester, 25,340 parts of acrylic acid, 440 parts of hydroquinone, 1,540 parts of concentrated sulfuric acid, and 9,760 parts of toluene were mixed, and the mixture was charged into a reaction vessel equipped with a stirrer, a thermometer, and a Dean-Stark trap. The reaction was continued for 5 hours at 0.degree. C. under reduced pressure while removing condensed water. The reaction is terminated when the distillation of condensed water stops, and the above reaction mixture is washed with alkali and water to remove unreacted acrylic acid and hydroquinone.
The toluene was then removed. The terminally acrylated polyester thus obtained was designated as resin (1). The cardinor viscosity of the resin (1) was 200 when the T1 double bond equivalent was measured by the PSDB method. In a similar manner, a polyester was obtained by condensing phthalic anhydride and diethylene glycol, and then acrylic acid was bonded to obtain a terminally acrylated polyester, which was designated as Jugetsu Den). This resin () had a cardinor viscosity of D and a double bond equivalent of 213. 35,700 parts of hydroxybivalyl hydroxybivalate (manufactured by Union Carbide, Ester Diol 204), 28,450 parts of acrylic acid, 650 parts of hydroquinone, 330 parts of concentrated sulfuric acid, and 8,200 parts of cyclohexane in a stirrer and a Dean Stark thermometer. 95-10 in a reaction vessel equipped with a type trap.
The reaction was continued at 0°C until no more condensed water was produced.

After the reaction is completed, the reaction solution is washed with alkali and water to remove the terminally reacted acrylic acid and hydroquinone, and then cyclohexane is removed to obtain acryloxypivalyl acryloxypivalate, which is mixed with resin (l
). This resin had a cardner viscosity of -A and a double bond equivalent of 162. Neopentyl glyconal 2
5,000 parts, acrylic acid 39,740 parts, hydroquinone 1,440 parts, p-toluenesulfonic acid 1,410 parts
Neopentyl glycol diacrylate was obtained by charging 7,060 parts of cyclohexane into a reaction vessel in the same manner as the method for producing resin (1), and obtaining resin QV).

This resin (5) had a cardner viscosity of -A and a double bond equivalent of 118. Add Cardiura E (Ciel Chemical) 225 to a reaction vessel equipped with a stirrer, thermometer, and condenser.
00 parts, 7,200 parts of acrylic acid, 600 parts of dimethylaminoethyl methacrylate, and 100 parts of hydroquinone monomethyl ether were charged, and the reaction was continued at 95 to 100°C until the acid value of the reaction solution reached 6.5. It stopped.

Thereafter, 6,370 parts of butyl acrylate was added to 20,000 parts of this Cardiura E acrylate.
Toluene diisocyanate (Takenate 80, manufactured by Takeda Pharmaceutical) 5,46 was maintained at 0°C and while blowing nitrogen gas.
0 part was added dropwise over 3 hours, and after the completion of the dropwise addition, the reaction was continued, and the reaction was completed when the remaining amount of isocyanate groups in the reaction solution became 1% or less. A butyl acrylate solution of Cardiula E acrylate urethane modified product was obtained, which was used as resin). This resin) was a viscous material with a cardner viscosity of U~. In a reaction vessel, 11,610 parts of 2-hydroxyethyl acrylate, 14 parts of phthalic anhydride,
810 parts of dimethylaminoethyl methacrylate, 100 parts of hydroquinone monomethyl ether, and 9,350 parts of butyl acrylate were charged and reacted at 100°C.
From the time when the acid value of the reaction solution reached 154, 14,220 parts of glycidyl methacrylate was added dropwise over 2 hours.
The reaction continued as it was, and the reaction was terminated when the acid value of the reaction solution reached 4.7.

A butyl acrylate solution of 2-acryloxyethyl 3-methacryloxy 2-hydroxypropyl phthalate was used as a resin.

The cardner viscosity of the resin (material) was D+. 31,100 parts of phthalic anhydride and 28,680 parts of ethylene glycol were placed in a reaction vessel equipped with a stirrer, a thermometer, a partial condenser, a total condenser, and a nitrogen gas introduction tube, and condensed at 210°C while blowing nitrogen gas. The reaction was continued while removing water and the reaction was terminated when the acid value of the reaction solution reached 0.4, yielding a polyester with a hydroxyl value of 450.

12,000 parts of this polyester, 9.6 parts of succinic anhydride
40 parts, 430 parts of dimethylaminoethyl methacrylate,
110 parts of hydroquinone monomethyl ether and 11,060 parts of butyl acrylate were charged into a reaction vessel equipped with a thermometer, a stirrer and a condenser, and reacted at 100°C. When the acid value of the reaction solution reached 159, glycidyl methacrylate 13, 680 parts of polyethylene phthalate was added dropwise over 2 hours, and the reaction was continued and the reaction was stopped when the acid value of the reaction solution reached 114.
A butyl acrylate solution of methacryloxy-2-hydroxypropyl succinate) was obtained and designated as Jugetsu Den).

The cardner viscosity of resin (4) was IT. 9,280 parts of 2-hydroxyethyl acrylate in a reaction vessel;
Phthalic anhydride 11,840 parts Dimethylaminoethyl methacrylate 210 parts Hydroquinone monomethyl ether 7
0 part was charged and reacted at 100℃, the acid value of the reaction solution was 216.
When the acid value of the reaction solution reached 8.6, 15,190 parts of an engineered poxy resin (Epicoat 4 #828 manufactured by Ciel Chemical Co., Ltd.) was added, and the reaction was stopped when the acid value of the reaction solution reached 8.6. Resin diluted with 9,180 parts of acrylate (to)
I got it.

(Vl) was a butyl acrylate solution of an epoxy resin modified with 2-acryloxyethylphthalic acid, and its cardner viscosity was V. Example 1 Jugetsuden 1) to (to) having a divalent (meth)acryloyl group in one molecule obtained in Example 1 are shown in Table-1.

Vinyl monomers made of (meth)acrylic acid esters and thermoplastic polymers were mixed in the proportions and combinations shown in Table 1 to produce syrups GJ) to (P). Titanium oxide: 47.51 parts per 100 parts of each of these syrups
part, chrome yellow - 2.16 parts, red iron 0.22 parts,
Enamel was obtained by mixing 0.11 parts of carbon black in a ball mill.

These enamels were applied to an asbestos slate plate using a roll coater to a thickness of 30 microns, and the coated plate was placed under an electron beam source and ionizing radiation was applied at 500KV135.
Electron beam irradiation was performed in an inert gas atmosphere at an irradiation dose of 5 mecarats under mA conditions.

Claims (1)

[Scope of Claims] 1 10 to 99% by weight of resins represented by the following structural formulas (A) to (H) having two (meth)acryloyl groups in 11 molecules, alone or in a mixture, and (meth)acrylic acid A surface-treated inorganic board characterized by coating an inorganic board with a composition comprising 0 to 50% by weight of esters and other vinyl monomers and 1 to 50% by weight of cellulose acetate butyrate, and then curing the composition by irradiating it with ionizing radiation. manufacturing method. (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (D) ▲There are mathematical formulas, chemical formulas, tables, etc. Yes (E) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (F) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (G) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (H) ▲ Mathematical formulas, chemical formulas, tables, etc. etc. ▼ Here, R_1 is H or -CH_3 R_2 is a divalent hydrocarbon (aliphatic,
alicyclic) residue or polyarykylene glycol residue R_3 having 1 to 10 ether bonds in the molecule is C_1_
~_1_0 divalent hydrocarbon residues (aliphatic, aromatic, alicyclic) R_4, R_5, R_6, R_7, R_1_2,
R_1_3 is H or C_1 to_8 substituted unsubstituted alkyl group, allyl group, cycloalkyl group R_8, R_9, R
_1_0, R_1_1, R_1_4, R_1_5, R_
1_6, R_1_7 is H or an alkyl group of C_1_ to C_8, an allyl group, a cycloalkyl group R_1_8 is C_3
or more straight chain or branched alkyl group or acyl group having C_3 or more straight chain or branched alkyl group R_1_9
There are ▲ mathematical formulas, chemical formulas, tables, etc. The alkylene group R_2_0 shown by ▼ is a C_1-_1_0 divalent hydrocarbon residue (aliphatic, aromatic) R_2_1 is H or the lower alkyl group R_2_2 is an acid anhydride of C_1-_1_0 Residue (aliphatic, aromatic, alicyclic)
The alkyl group R_2_5 of _1 to _1_8 has ▲ mathematical formula, chemical formula, table, etc. ▼ n = integer k of 0 to 14, l, m, o, p, q, r, s, t = integer u of 0 to 5
= 0 or 1v = integer from 1 to 20 w = integer from 0 to 20