JPH0218410A - Method for imparting stain resistance to base material - Google Patents

Abstract

PURPOSE:To obtain a whiteboard excellent in erasability of a marker therefor and free from deterioration of the erasability even under a long term service by forming a coating film prepared by curing a specified copolymer using a metal chelate compound on the surface of the base material. CONSTITUTION:With 70-99.999mol% compound of formula I (R1 is 1-8C aliphatic hydrocarbon or phenyl; R2-R4 are 1-4C alkoxy or OH) 30-0.001mol% compound of formula II (R5 is H or methyl; R6-R8 are OH, 1-4C alkoxy, etc.; n is 1-6) is initially reacted to prepare a polysiloxane-based macromonomer with 400-100,000 number-average molecular weight and >=2 free functional groups selected from OH and alkoxies. A coating film is then formed on the surface of the base material by curing a copolymer composed of the above-mentioned macromonomer and an oxirane group-containing vinyl monomer as the monomer components with a metal chelate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for imparting stain resistance to a substrate, and more particularly, to a whiteboard with particularly excellent erasability.

(Prior art and its problems) Conventional materials used for whiteboards include (1) a cured layer of melamine resin, (2) a cured layer of polyisocyanate-polyol resin, (3) a cured layer of a low condensate of alkyl alkoxysilane, and (4) There is a product provided with an active energy ray-cured resin layer. However, in method (1), generally high temperatures (approximately 14
0°C or higher), it is difficult to apply to substrates such as plastics with a low thermal deformation temperature, or substrates such as wood or inorganic materials with poor thermal conductivity, and method (2) Then, the erasability of whiteboard markers is inferior,
Another disadvantage is that the erasability deteriorates during long-term use, and yellowing occurs due to ultraviolet rays and sunlight during long-term use. A large amount of condensate causes defects such as cracks in the cured layer, resulting in poor appearance of the whiteboard and poor physical properties, and (4)
In this method, the cost of the irradiation equipment that generates ultraviolet rays and electron beams is high, making the resulting product expensive and impractical.Also, since epoxy acrylate resin is used as the resin, it will not last long after use. It has the disadvantage of yellowing due to ultraviolet rays and sunlight.

The present invention provides a whiteboard that has excellent erasability after writing with a whiteboard marker and has excellent durability without degrading the erasability even after long-term use.

(Means for Solving the Problems) The present inventor has conducted extensive research in order to solve the problems of the prior art as described above. As a result, a vinyl copolymer containing a specific polysiloxane macromonomer having two or more free functional groups such as a hydroxyl group or an alkoxyl group and an oxirane group-containing vinyl monomer as a monomer component can be used as a metal chelate compound. In the presence of the vinyl copolymer, the silanol groups present in the polysiloxane macromonomer that is the monomer component of the vinyl copolymer and the silanol groups generated by hydrolysis of the alkoxyl groups in the macromonomer, and the silanol groups in the oxirane group-containing vinyl monomer. The oxirane group becomes a crosslinking functional group, and it cures easily to form a vehicle-cured film even at low temperatures of 100° C. or lower, and the vehicle-cured film has excellent erasability after being written with a whiteboard marker.

In addition, they discovered that it itself exhibits excellent physical properties, leading to the completion of the present invention.

That is, the present invention provides a substrate surface with (i) or a hydroxyl group, 70 to 99.999 mol% of compound (A) represented by the general formula % formula % () c In the formula, R6 represents a hydrogen atom or a methyl group, R6, R
7 and R1 represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, provided that
R, R, and R8 are not all aliphatic hydrocarbon groups having 1 to 8 carbon atoms, n represents an integer of 1 to 6,
) is reacted with 30 to 0.001 mol% of the compound (B) represented by (B), has two or more free functional groups per molecule selected from hydroxyl groups and alkoxyl groups, and has a number average molecular weight of 400. -100,000 and (ii) a copolymer containing an oxirane group-containing vinyl monomer as a monomer component, which is cured with a metal chelate compound to provide stain resistance to the substrate. Concerning the method of imparting gender.

In the method of the present invention, R6 (a polysiloxane macromonomer which is a monomer component of a vinyl copolymer used as a fat component) has a main skeleton composed of siloxane bonds, and Si of this main skeleton has an aliphatic hydrocarbon group, phenyl group, hydroxyl group,
An alkoxyl group, a polymerizable unsaturated bond, etc. are bonded directly or indirectly, and is represented by -R9 formula % formula % () (in the formula, R1, R2, R8 and R4 are the same as above) It can be obtained by reacting the compound (A) represented by the following formula with the compound (B) represented by the general formula (wherein R1, R6, R1, R, and n are the same as above).

In the above compound (A), R1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R2, R8, and R4 represent an alkoxyl group or a hydroxyl group having 1 to 4 carbon atoms. R4 may be all the same or may be partially or entirely different.

In compound (A), examples of the alkoxyl group having 1 to 4 carbon atoms include linear or branched ones such as methoxy, ethoxy, propoxy, and butoxy groups; Examples of the aliphatic hydrocarbon group 8 include straight chain or branched aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group.

In the above compound (A), R1 is particularly preferably a methyl group or phenyl group, and Rg, R3, and R4 are particularly preferably a methoxy group, ethoxy group, propoxy group, butoxy group, or hydroxyl group. Preferred specific examples of compound (A) Examples include methyltrimethoxysilane, phenyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, methyltriptoxysilane, phenyltrisilanol, methyltrisilanol, and the like. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, phenyltrisilanol and the like are particularly preferably used. Compound (A) can be used alone or in combination.

In the above compound CB), R6 represents a hydrogen atom or a methyl group, R,, R, and R8 are a hydroxyl group, and have 1 to 4 carbon atoms.
represents an alkoxyl group or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 6. R6, R2 and R8
may be all the same or partially or entirely different, but all must not be aliphatic hydrocarbon groups having 1 to 8 carbon atoms.

The aliphatic hydrocarbon group having 1 to 8 carbon atoms and the alkoxyl group having 1 to 4 carbon atoms in compound (B) include the compound (
Items similar to those in A) can be mentioned.
As IRII, R7 and R6, methoxy group, ethoxy group, and hydroxyl group are particularly preferable, and n is particularly preferably in the range of 2 to 4. Preferred specific examples of compound (B) include γ-metacycloxypropyltrimethoxysilane, Examples include γ-metacycloxypropyltriethoxysilane, γ-acycloxypropyltrimethoxysilane, γ-metacycloxybutyltriethoxysilane, γ-acycloxypropyltrisilanol, and the like. Among these, γ-metacycloxypropyltrimethoxysilane, γ-metacycloxypropyltriethoxysilane, γ-acycloxypropyltrisilanol, etc. are particularly preferred, and the compound (B
) can be used alone or in appropriate combination.

In the present invention, the polysiloxane macromonomer is
The mixing ratio of the two compounds obtained by mixing and reacting the above compound (A) and compound (B) is based on the total amount of the compounds in between, and the compound (A) is 70 to 9
9.999 mol%, preferably 90 to 99.9 mol%,
More preferably 95 to 99 mol%, compound (B) is 3
0 to 0.001 mol%, preferably IO to 0.1 mol%
, more preferably within the range of 5 to 1 mol%. If the compound (A) is outside the above range, it is not preferable because a whiteboard with excellent appearance cannot be obtained.

The reaction between compound (A) and compound (B) is carried out by dehydration condensation of the hydroxyl group of the intermediate compound or the hydroxyl group generated by hydrolysis of the alkoxyl group. At this time, depending on the reaction conditions, not only dehydration condensation but also partial dealcoholization condensation occurs.

Although this reaction can be carried out without a solvent, it is preferable to carry out the reaction using an organic solvent that can dissolve compound (A) and compound (B), or water. As such an organic solvent, heptane is preferably used. , hydrocarbon solvents such as toluene, xylene, octane, mineral spirits, etc.
Ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate, butylcarpitol acetate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Ethanol, isopropanol, n-butanol, 5e
Alcohol solvents such as e-butanol and isobutanol, ether solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether can be used. These solvents can be used alone or in appropriate combinations.

When used in a solution state, the concentration of compound (A) and compound (B) is suitably about 5% by weight or more in total.

In the reaction between compound (A) and compound (B) in the present invention, the reaction temperature is usually about 20 to 180°C, preferably about 50 to 120°C. Moreover, it is appropriate that the reaction time is usually about 1 to 40 hours.

In addition, in this reaction, a polymerization inhibitor may be added as necessary.6 The polymerization inhibitor is a polymerization inhibitor that prevents unsaturated bonds contained in compound (B) from polymerizing during the reaction with compound (A). Specifically, hydroquinone, hydroquinone monomethyl ether, etc. can be used.

In addition, in the production of this polysiloxane-based macromonomer, there is no problem in further adding tetraalkoxysilane, dialkyldialkoxysilane, etc. to the reaction system of the above compound (A) and compound (B), and the intervening compound 2
It can be added in an amount of about 0 mol% or less.

Upon reaction of compound (A) and compound (B), R8,
When R3, R4, Rs, Ry and R8 are all hydroxyl groups, it is preferable to carry out dehydration condensation in an organic solvent under heating and stirring.

Further, the compound (A) and/or the compound (B) may be Si
When it has an alkoxyl group bonded to, it is preferable to hydrolyze it prior to condensation, and the hydrolysis reaction and condensation reaction can be carried out continuously by heating and stirring usually in the presence of water and a catalyst. The amount of water used in this case is not particularly limited, but it is preferably about 0.1 mol or more per 1 mol of alkoxyl group; if it is less than about 0.1 mol, the reaction of the intercompound may decrease. . The most preferred method is to use water as a solvent in large excess. Further, in this reaction, if water and a water-soluble organic solvent are used together, the reaction system can be made homogeneous when an alcohol that is sparingly soluble in water is produced by condensation. As the water-soluble organic solvent, the above-mentioned alcohol-based, ester-based, ether-based, ketone-based, and other solvents can be preferably used. As a catalyst for this hydrolysis reaction, an acid catalyst or an alkali catalyst can be used. Specifically, acid catalysts include hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid,
Acrylic acid, methacrylic acid, etc. can be used, and sodium hydroxide, triethylamine, ammonia, etc. can be used as an alkali catalyst. The amount of catalyst added is determined by the amount of the above compound (A
) and compound (B), 0.0001 to 5
A suitable amount is about 0.01 to 0.1% by weight, preferably about 0.01 to 0.1% by weight.

In the present invention, the polysiloxane macromonomer used has a number average molecular weight of about 400 to 100,000, preferably about 1,000 to 20,000. If the number average molecular weight is less than about 400, the physical properties of the film will be poor and a whiteboard with excellent flexibility cannot be obtained;
If it exceeds about 0.00, the surface smoothness of the whiteboard will be poor, and the ease of writing and erasing of the whiteboard marker will tend to deteriorate, which is not preferable.

In the present invention, the main skeleton of the polysiloxane macromonomer obtained by the reaction of compound (A) and compound (B) is constituted by siloxane bonds, and the structure of the main skeleton is mainly linear or ladder-like. (1a
dder) or a mixture of these. Among these, whiteboard markers with a ladder-like structure or a mixed system with many ladder-like parts are superior in erasability, and even after long-term use, the marker remains intact. These structures are preferable because a whiteboard with excellent durability can be obtained without deterioration of erasability. can be selected arbitrarily. Then, the polysiloxane-based macromonomer connects the Si of this siloxane bond to either R+ or Ra-R4 of the above-mentioned -killing (I) and (1), CH2=C-
Coo (CHI) A structure in which any of n, R, ~R, etc. are bonded, and a free functional group such as a hydroxyl group bonded to Si and/or an alkoxyl group having 1 to 4 carbon atoms (i.e. , silanol group and/or alkoxysilane group) per molecule.

Further, the polysiloxane macromonomer preferably has an average of 0.2 to 1.9 polymerizable unsaturated bonds per molecule, more preferably 0.6 to 1.4, It is most preferable to have 0.9 to 1.2 pieces.

Examples of the epoxy group-containing vinyl monomers include alicyclic epoxy group-containing vinyl monomers represented by the following formulas (II+) to (X Vll ).

[In each case, R9 represents a hydrogen atom or a methyl group, R
6° represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, Ro represents a divalent hydrocarbon group having 1 to 10 carbon atoms,
I2 represents an integer of 0 to 20, 1 In the above, the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R1° is a linear or branched alkylene group such as methylene, ethylene, , propylene, tetramethylene, ethyl ethylene, pentamethylene,
Examples include hexamethylene group. Also, Ro
Examples of the divalent hydrocarbon group having 1 to carbon atoms include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, -()→,
CH2-C)-CHz- group and the like can be mentioned.

Typical vinyl monomers containing non-alicyclic epoxy groups include those represented by the following formula (X).

In formula 1, R- and R1° are the same as above. Among the above-mentioned epoxy group-containing vinyl monomers, vinyl monomers containing an alicyclic epoxy group are particularly used for whiteboard markers. It is preferable because it has excellent erasability and durability of the erasability.

The resin component used in the present invention is a vinyl copolymer using the above-mentioned polysiloxane macromonomer and an oxirane group-containing vinyl monomer as monomer components. In the copolymer, other polymerizable monomers may be used as monomer components in addition to the above-mentioned monomer components, if necessary.

Such other polymerizable and nyl monomers can be selected from a wide range depending on the desired performance. Representative examples of such unsaturated monomers are as follows.

(a) Esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylate. C1-18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate: methoxybutyl acrylate, methacrylic acid Alkoxyalkyl esters having 2 to 18 carbon atoms of acrylic acid or methacrylic acid such as methoxybutyl, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate: Acrylic acid such as allyl acrylate and allyl methacrylate; Alkenyl esters of methacrylic acid having 2 to 8 carbon atoms: Hydroxy alkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate: allyloxyethyl acrylate; Alkenyloxyalkyl esters of acrylic acid or methacrylic acid having 3 to 18 carbon atoms, such as allyloxymethacrylate.

(b) Vinyl aromatic compounds: for example, styrene, a
-Methylstyrene, vinyltoluene, p-chlorostyrene.

(c) Polyolefin compounds: for example, butadiene, isoprene, chlorobrene.

(d) Others: Acrylonitrile, methacrylaterile, methyl isopropenyl ketone, vinyl acetate beoba monomer (Shell Chemical Products), vinyl propionate,
vinyl vivarate etc.

In the vinyl copolymer used in the present invention, the amount of each monomer used is from 0.01 to 0.01 for the vinyl copolymer consisting of two components, a polysiloxane macromonomer and a vinyl monomer containing an oxirane group. 98% by weight and the latter 99.9%
9 to 2% by weight, preferably 0.1 to 80% by weight of the former and 99.9 to 20% by weight of the latter. If the amount of polysiloxane macromonomer used is less than this range, the mechanical strength and weather resistance of the whiteboard will be poor, and the erasability and durability of the whiteboard marker will tend to decrease, and if the amount exceeds this range This is undesirable because it reduces the mechanical strength, appearance, etc. of the whiteboard, and also reduces the erasability and durability of the whiteboard marker.

In addition to the above two types of monomers, when using other polymerizable vinyl monomers as a monomer component, the polysiloxane macromonomer should be used in an amount of 0.01 to 80% by weight, preferably 0.1 to 60% by weight. %, oxirane group-containing vinyl monomer 1-90% by weight, preferably 3-60% by weight, other polymerizable vinyl monomers 0-98.991if(i%,
Preferably it is 10 to 96.9% by weight. It is not preferable to use the polysiloxane macromonomer and the oxirane group-containing vinyl monomer in amounts outside this range for the same reasons as above.

The above copolymer has a number average molecular weight of 3,000 to 200,000.
It is preferably about 10,000 to about 80,000, more preferably about 10,000 to 80,000.

In the present invention, in addition to the above-mentioned vehicle components, a homopolymer of the polysiloxane macromonomer or a copolymer of the polysiloxane macromonomer and the other polymerizable vinyl monomer (simply referred to as " A homopolymer of the above-mentioned oxirane group-containing vinyl monomer or a copolymer of the oxirane group-containing vinyl monomer and other polymerizable vinyl monomer [this product is simply referred to as It can be used in combination with ``polymer (b)''. The mixing ratio of the polymers is 5 to 95% by weight of polymer (a) and 95% by weight of polymer (b) in the total amount of both.
~5% by weight range.

In the present invention, at least one of an aluminum chelate compound, a titanium chelate compound, and a zirconium chelate compound is used as a crosslinking reaction curing agent. Further, among these chelate compounds, a chelate compound containing a compound capable of forming a keto-enol tautomer as a ligand forming a stable chelate ring is preferred.

Compounds that can constitute keto-enol tautomers include β-diketones (acetylacetone, etc.), acetoacetic esters (methyl acetoacetate, etc.), malonic acid esters (ethyl malonate, etc.), and Ketones having a hydroxyl group (such as diacetone alcohol), aldehydes having a hydroxyl group at the β position (such as salicylaldehyde), esters having a hydroxyl group at the β position (methyl salicylate), and the like can be used. In particular, acetoacetic acid esters, β
- Favorable results are obtained using diketones.

The aluminum chelate compound has, for example, the general formula OR+! Rl-0-A! -0Rta (X
IX) [wherein R1 represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms, a compound capable of forming the above keto-enol tautomer per mol of the aluminum alcoholade represented by J It can be suitably prepared by mixing them at a molar ratio of usually about 3 moles or less and heating if necessary.

As the alkyl group having 1 to 20 carbon atoms, the above-mentioned alkyl group having 1 to 20 carbon atoms
In addition to the alkyl group of 6, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, octadecyl group, etc., as alkenyl group,
Examples include vinyl and allyl groups.

The aluminum alcoholades represented by the general formula (xrx) include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum Examples include aluminum tri-5ec-butoxide, aluminum tri-tert-butoxide, etc., and it is particularly preferable to use aluminum tri-5ee-butoxide, aluminum tri-5ee-butoxide, aluminum tri-tert-butoxide, and the like.

The titanium chelate compound can be, for example,
represents an alkyl group or an alkenyl group.] To 1 mol of Ti in the titanate represented by the above, a compound capable of forming the above keto-enol tautomer is mixed at a molar ratio of usually about 4 mol or less, and the necessary It can be suitably prepared by heating according to the conditions. Carbon number 1~
The alkyl group and alkenyl group of 20 are the same as above.

- 1m for titanates expressed by XX
is 1, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert
-butyl titanate, tetra-n-pentyl titanate, tetra-n-hexyl titanate, tetra-isooctyl titanate, tetra-n-lauryl titanate, etc., especially tetra-isopropyl titanate.

Suitable results are obtained using tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-tert-butyl titanate, and the like. For those with %m of 1 or more, tetraisopropyl titanate, tetra-n
Dimers to 11-mers of -butyl titanate, tetraisobutyl titanate, and tetra-tert-butyl titanate (m=1 to 10 in -killing (XX)) give preferable results.

The zirconium chelate compound is, for example, -Sakatsu 1, where m is an integer of 0 to 1O, and R14 is a carbon number of 1 to 20.
represents an alkyl group or an alkenyl group, ] to 1 mol of Zr in the zirconate represented by the following, the above-mentioned compound capable of forming the keto-enol tautomer is mixed at a molar ratio of usually about 4 mol or less, and as necessary. The alkyl group and alkenyl group having 1 to 2.0 carbon atoms are the same as those described above.

- Zirconates represented by XI (X -butylzirconate, tetra-n-pentylzirconate, tetra-te
rt-pentylzirconate, tetra-tert-hexylzirconate, tetra-n-hebutylzirconate, tetra-n-octylzirconate, tetra-n-
Stearyl zirconate, etc., especially tetraisopropyl zirconate, tetra-n-propyl zirconate, tetraisobutyl zirconate, tetra-n-butyl zirconate, tetra-5ec-butyl zirconate,
Suitable results are obtained using tetra-tert-butyl zirconate and the like. In addition, for those where m is 1 or more, tetraisopropyl zirconate, tetra-n-propyl zirconate, tetra-n-butyl zirconate, tetra-isobutyl zirconate, tetra-3eC-butyl zirconate, tetra-tert-butyl 1131 bodies from the dimer of zirconate (-slaughter (X XI)
m=1-10) gives suitable results.

Further, it may contain a structural unit in which these zirconates are associated.

Particularly preferred chelate compounds in the present invention include diisopropylate ethyl acetoacetate aluminum, tris(ethyl acetoacetate) aluminum, tris(n-propylacetoacetate) aluminum, tris(isopro and ruacetoacetate) aluminum, Tris (n-butylacetoacetate) aluminum, isopropoxybisethylacetoacetate aluminum, diisopropoxyethylacetoacetate aluminum, tris (acetylacetonato) aluminum, tris (ethylacetonato) aluminum, diisopropylate ethylacetonate aluminum, Monoacetylacetonate bis(ethylacetonato)aluminum, monoethylacetoacetate bis(acetylacetonato)aluminum, tris(isopropylate)aluminum, tris(see-butyrate)aluminum, diisopropylate mono-5ec
-butoxyaluminum, tris(acetylacetone)
Aluminum chelate compounds such as aluminum; titanium chelate compounds such as diisopropoxy bis(ethylacetoacetate) titanate, diisopropoxy bis(acetylacetate) titanate, diisopropoxy bis(acetylacetone) titanate: tetrakis(acetylacetone) zirconium , tetrakis (n
Zirconium chelate compounds such as -pro- and ru-acetoacetate) zirconium, tetrakis (acetylacetonato) zirconium, and tetrakis (ethylacetoacetate) zirconium can be mentioned.

In the present invention, as a crosslinking reaction curing agent, any one of an aluminum chelate compound, a zirconium chelate compound, and a titanium chelate compound may be used, or two or more types may be used in combination as appropriate. The amount is 0.01 to 3 parts by weight per 100 parts by weight of the polymer.
Appropriately, the amount is approximately 0 parts by weight.

If necessary, extender pigments, coloring pigments, dyes, etc. can be added to the whiteboard formed by the method of the present invention. In addition, if necessary, -functional or polyfunctional epoxy compounds, low molecular weight silane compounds such as triphenylmethoxysilane, diphenyldimethoxysilane, etc.
- Other resins can also be added, such as silicone resins with numerical alkoxysilane groups.

The method of the present invention can be carried out by applying a composition prepared by blending the above polymer with a metal chelate compound onto the surface of the material and drying it. Examples of the material include plywood, synthetic wood, wood, laminate board, paper, metal plate, inorganic material (eg, calcium silicate board, concrete, etc.), plastic molded product, plastic board, and sheet magnet. Examples of coating methods include roll coating, reverse roll coating, knife coating, curtain flow coating, spray coating, dip coating, flow coating, and brush coating to form a dry film of about 1 to 40%. Apply to a thickness of 200μ, preferably in the range of about 10 to 100μ.

Drying is usually done at room temperature for 8 hours to 7 days or about 40 days.
It can be fully cured in about 5 minutes to 3 hours by heating at ~100°C.

In the present invention, for the purpose of improving the adhesion between the material and the cured layer, conventionally known brimers such as vinyl acetate, polyvinyl chloride, vinyl acetate-vinyl chloride copolymer,
Acrylic urethane resin, polyester resin, etc. can be used.

The coating obtained by the method of the present invention can be formed on objects that require stain resistance, and is particularly effectively used as whiteboards for teaching materials, conferences, exhibitions, etc.

(Effects of the Invention) As described above, the method of the present invention has the following remarkable effects compared to the conventional method.

l) A cured layer with excellent curability is formed on inorganic materials with a large heat capacity, and even on materials such as sheet magnets with a low thermal deformation temperature, the material does not undergo thermal deformation and has an excellent appearance. A layer can be formed.

2) A hardened layer formed on a material such as a sheet magnet does not produce defects such as cracking or peeling even when subjected to severe processing deformation such as bending or impact.

3) A whiteboard having the hardened layer on its surface has excellent erasability of whiteboard markers, and even after long-term use, this erasability hardly deteriorates.

4) Since the whiteboard does not undergo deterioration such as discoloration or deterioration even when exposed to fluorescent lights, sunlight, etc., it can maintain its excellent cosmetic properties for a long period of time.

(Example) Examples of the present invention are shown below.

Example 1 deionized water 60% hydrochloric acid hydroquinone 134g g g These mixtures were reacted at 80°C for 5 hours.

The obtained polysiloxane macromonomer had a number average molecular weight of 2000, and had on average one vinyl group (polymerizable unsaturated bond) and four hydroxyl groups per molecule. 300g of this macromonomer and styrene
too g glycidyl methacrylate
100gn-butyl methacrylate 500
g A mixture of 20 g of azoisobutyronitrile was added dropwise to 1000 g of xylene at 120° C. and polymerized to obtain a transparent copolymer. Number average molecular weight is approximately 2000
It was 0.

200 g of this resin solution and titanium white pigment (50 g mixed for 100 g of W fat) were mixed and dispersed, and the composition was applied to a calcium silicate plate to a film thickness of 50 μm (dry).
It was baked at 100°C for 30 minutes.

Example 2 γ-Acycloxypropyl 200g Trisilanol (1mol) Toluene
4500 g of these mixtures were reacted at 11"7°C for 3 hours and dehydrated. The number average molecular weight of the obtained polysiloxane macromonomer was 700.
0, on average had one vinyl group and 5 to 10 hydroxyl groups per molecule. 100g of this macromonomer and 2
-Hydroxyethyl acrylate 100 g (2-Ethylhexyl methacrylate) 600 g Azoisobutyronitrile A mixture of 10 g was added dropwise into 1000 g of an equal weight mixture of butanol and xylene at 120°C and polymerized to obtain a transparent copolymer. . The number average molecular weight was approximately 40,000.

200g of this resin solution and titanium white pigment (hA fat 100g)
0.3 g of tetrakis(acetylacetone) zirconium was added to this mixture. The composition was placed on a polyvinyl chloride plate at 50 μm.
It was applied to a film thickness (dry) of 100.degree. C. and baked for 30 minutes at 80.degree. C. to obtain a whiteboard. The whiteboard had no defects such as deformation or distortion and had a good appearance.

Example 3 29.1 mol of methyltrimethoxysilane and 0.9 mol of γ-acyclooxyethyltriethoxysilane were added in Example 1.
The reaction was carried out in the same manner. The number average molecular weight of the obtained polysiloxane macromonomer was about 15,000, and on average, one vinyl group and one methoxy group were contained in a concentration of 5 to 1 O per molecule.
It was unique. 400 g of this macromonomer and Example 1
600 g of the vinyl monomer used in Example 1 was polymerized in the same manner as in Example 1 to obtain a copolymer. The number average molecular weight was approximately 70,000.

After mixing and dispersing 200 g of this resin solution and a titanium white pigment (50 g mixed per 100 g of resin), 10 g of tetrakis (ethylacedoacet) zirconium was added to the mixture. The composition was applied to one side of a magnetic sheet with a thickness of about 1 mm to a film thickness of 50 μm (dry).
Baking for 30 minutes at 0°C yielded a whiteboard. There were no defects such as deformation or distortion of the whiteboard, and it had a good appearance.

Example 4 2-hydroxyethyl methacrylate 100 g2
- Ethylhexyl methacrylate 500 g Styrene 150 g Azoisobutyronitrile A mixture of 10 g in 1000 g of an equidistant mixture of n-butanol and xylene 120 g
It was added dropwise at ℃ to obtain a transparent copolymer. The number average molecular weight was approximately 40,000.

After mixing and dispersing 200 g of this resin solution and a titanium white pigment (50 g mixed per 100 g of resin), 0.5 g of diisopropoxy bis(acetylacetone) thicnate was added. The composition was applied to one side of a 150 μm thick double-sided art paper to a film thickness of 50 μm (dry) and baked at 80° C. for 30 minutes to obtain a whiteboard. The whiteboard had a good appearance with no defects such as deformation or distortion.

Comparative Example 1 Acrydique A-801p (manufactured by Dainippon Ink Co., Ltd., trade name, acrylic polyol) looog and titanium white pigment (
After mixing and dispersing 50g of resin per 100g of resin, 90% by weight of Burnock DN-990 (manufactured by Dainippon Ink Co., Ltd., trade name, diisocyanate compound) 17
A two-modified composition containing 8 g of xylene and 142 g of xylene was applied to a magnetic sheet to a dry film thickness of 10 μm, and baked at 80° C. for 30 minutes to obtain a whiteboard.

Comparative example 2 136 g of methyltrimethoxysilane, 29 g of deionized water
, O,IN A mixture of 1.6 g of hydrochloric acid and 250 g of ethanol was stirred at 50"C for 6 hours, and the resulting solution and titanium white pigment (50 g mixed for 100 g of resin) were mixed and dispersed, and then a magnetic sheet was prepared. It was applied to a dry film thickness of 10 μm and baked at 80° C. for 30 minutes to obtain a whiteboard.

The test results are summarized in the table.

Test method Ease of writing with markers: The sharpness of lines and letters when drawn with three colored markers, black, blue, and red, was evaluated. (○: Good,
Δ: Slightly inferior, ×: Poor) Marker erasability (initial): After writing lines and characters with black, blue, and red markers, erase them with a whiteboard eraser, and repeat this process 10,000 times in the same place. The appearance after cycling and finally wiping with an eraser was evaluated.

(○: Marker marks do not remain, ■ = Mom-- traces remain slightly, Δ: Marker marks remain, ×: Significant marker marks remain) Marker erasability (after weather resistance): The following After conducting the same weather resistance test, the erasability of the marker was examined in the same manner as above.

Bending: After bending 180°, the presence or absence of abnormalities such as cracks and peeling on the surface was visually evaluated.

Weather resistance: QUV weather meter manufactured by The Q Panel (UV fluorescent lamp r No, Q F S-40, UV
-BJ, wavelength range 320-280 nm) at a temperature of 40-70 °C (15
After repeating the cycle of 1 minute) and 15 minutes for 5000 hours, the degree of deterioration of the whiteboard surface was observed.

Claims (1)

[Claims] 1. On the surface of the base material (i) there is a general formula▲mathematical formula, chemical formula, table, etc.▼・・・・・・(I
(In the formula, R_1 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a phenyl group, and R_2, R_3, and R_4 represent an alkoxyl group or hydroxyl group having 1 to 4 carbon atoms.) Compound (A) represented by 70 to 99.999 mol% and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ...... (II) (In the formula, R_5 is a hydrogen atom or a methyl group, R_6
, R_7 and R_8 represent a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms, or an aliphatic hydrocarbon group having 1 to 8 carbon atoms. However, R_6, R_7 and R_8 all have 1 carbon number.
~8 aliphatic hydrocarbon groups. n represents an integer of 1 to 6. ) is reacted with 30 to 0.001 mol% of the compound (B) represented by (B), has two or more free functional groups per molecule selected from hydroxyl groups and alkoxyl groups, and has a number average molecular weight of 400. -100,000 and (ii) a copolymer containing an oxirane group-containing vinyl monomer as a monomer component, which is cured with a metal chelate compound to provide stain resistance to the substrate. How to give gender.