JPS6348364A - Silane coating composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which gives a coating film having excellent mar resistance, antistatic properties, etc., containing a specified organosilane compd. having hydroxyl group (hydrolyzate) and a silane compd. (hydrolyzate) in a specified weight ratio as film forming components. CONSTITUTION:The title compsn. contains 5-80wt% hydroxyalkylhydroxysilane (A) of formula I (wherein n is 1-6; m is 1-3) and/or hydrolyzate (A) of an organosilane compd. having hydroxyl groups, represented by formula II (wherein R is a 1-4C alkyl or acetyl) and 95-20wt% hydroxysilane (B) of formula III (wherein R' is a 1-6C alkyl which may be substituted with a halogen, amino, glycidyl or mercapto group, a cycloalkyl, an alkenyl or an aryl; l is 0-3) and/or hydrolyzate (B) of a silane compd. of formula IV (wherein R<2> is a 1-6C alkyl or acetyl) as film forming components.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silane-based coating composition that has excellent scratch resistance, antistatic properties, transparency, and the like.

BACKGROUND ART Synthetic resins generally have a disadvantage in that they are easily damaged due to their lower surface hardness than other materials such as glass and metals. In addition, due to its high electrical insulation properties, it is easily charged with static electricity.
It also has the disadvantage that it is easy for dust etc. to stick to it. When wiping off this adhered dust with a cloth or the like, abrasions are likely to occur on the surface of the synthetic resin, and further electrification is caused by wiping, leading to a vicious cycle in which dust adheres.

In order to solve these problems with synthetic resins, methods have been used to improve the properties of the resin surface by coating the resin surface with a coating composition to form a film.

For example, in order to improve the surface hardness of a synthetic resin and improve the scratch resistance of the resin surface, a UV-curable coating agent such as silicone resin or acrylic urethane with a high crosslinking density is applied to the resin surface. A method of forming a film is adopted. However, when such a coating agent is used, although it is possible to improve the scratch resistance of the resin surface, it is not possible to improve the antistatic property.

On the other hand, methods to improve antistatic properties include coating the resin surface with a surfactant or silicate compound, or
A method of applying a paint mixed with metal or gold B4 oxide; #IF is known. However, in the method using a surfactant or a silicate compound, the sustainability of the antistatic effect is insufficient, and the scratch resistance cannot be sufficiently improved. In addition, a method using a paint mixed with metal or metal oxide cannot form a film with good transparency. In this way, a method using a conventional coach ink composition does not allow scratch resistance on the surface of a synthetic resin molded object. At present, it is not possible to form a film that can improve the properties and antistatic properties at the same time and has good transparency.

In view of the above-mentioned current situation, the present inventor has created a film that can maintain the effects of improving both the scratch resistance and antistatic properties on the surface of a synthetic resin molded article over a long period of time, and has excellent transparency. We have been conducting extensive research to find a coating agent that can achieve this goal. As a result, it was discovered that the desired objective could be achieved when two types of specific silane compounds were used in combination as a coating film forming component, and the present invention was thus completed.

Uchi, the present invention has cA) a) General formula: (HO<C1f2>N')mSI
<OH>,, -m (in the formula, N is an integer of 1 to 6, m is 1 to 3
(indicating an integer of
R) Hydrolyzate of an organosilane compound containing a dro+oxy group, represented by 4-m (wherein R represents an alkyl group or an acetyl group having 1 to 4 carbon atoms, and 〃 and m are the same as above) , and @J) General formula: R” lSr (QH) a
g (where R1 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group having 1 to 6 carbon atoms). It may have a substituent selected from halogen, atricidyl, talicidyl and mercapto group. l represents an integer of 0 to 3), and/or b) General formula: R11S' (0R2)a g (wherein R2 is an alkyl group having 1 to 4 carbon atoms) A silane compound consisting of a hydrolyzate of a silane compound represented by 1 or an acetyl group, R1 and 1 are the same as above) is used as a coating film-forming component, and (HO(C
〕12)□〕I SJ (QH) 4-9 and/or (1
10<CH2>, l'JMSi<OR>4-,,5-8
0 fflfa%, R11S' (OB) a-i and/or RleSr (0R2) a J 20-9
5% by weight of a silane-based coachinter composition.

The coating film-forming component in the coating composition of the present invention has the general formula 2 (HO(C)'2)jl)mSJ (0
7/ ) i, -1(1) (wherein R and m are the same as above) and/or the general formula: (HO(C112>g)m Si<oR >4
-4 (2) A hydrolyzate of an organic silane compound containing a silane group and a silane group represented by the formula (2) (in the formula, human, m and rhinoceros are the same as above) is used.

-1 carbon number represented by R in the compound of general formula (2)
As the alkyl group of ~4, linear or branched al+
Methyl, ethyl)prodyl 1
Examples include isobutyl (5ff-butyl), 5ee-butyl, tart-butyl, and the like.

Specifically, the human 0 ox siloxyl silane expressed by the general formula (1) in the above prison component includes human 0 ox silox 0 pill (trihuman 0 ox sil) silane, dihydro silox 0 silane ( Jishido 0shishi) Shiran, Torihito 0shishibu Ogor (shidoro + Shi) Shira: J) Human 0 cow diptyl (Torihito 0shishi) Silan, Jishido 0shi diptyl (Jishidoro cowshi) ) silane, dibutyl silane, etc. can be exemplified. Examples of the organic silane compounds containing Noji0+Si groups of general formula (2) include Shido0gyushibu0pil (Trimethogyushi) silane, Toshidoroshi Ciprohil (Ashichitogyushi) silane, Shidoro+Diptyl ( triet + ci) silane,
Examples include dihydro+diptyl (,;but+sil) silane, trihydro+diptyl (meth+sil) silane, and the like.

The compound of general formula (1) can be used as it is, but the organic silane compound containing a perilla group of general formula (2) needs to be used as a hydrolyzate. The hydrolysis method is not particularly limited, and generally known methods can be employed. For example, neutral water or water made acidic by adding hydrochloric acid may be added to perform hydrolysis at room temperature. General formula (
The compound 2) may not be completely hydrolyzed, or may be only partially hydrolyzed. Moreover, a part of the compound of general formula (2) may be partially condensed due to hydrolysis, but even in such a state, it can be suitably used as a coating film-forming component.

In addition, as the @component of the coating film forming component, the general formula: R"
JSr (OH)at (3) (wherein R1 and l are the same as above), and/or the general formula: R"ls r (0R2)4J (4
) (wherein B1.B2 and l are the same as above) is used.

In the compounds of general formulas (3) and (4), the alkyl group at carbon atoms W11 to W6 represented by R1 may include straight or branched alkyl groups, such as methyl, ethyl 1 isobutyl (N-butyl) isobutyl,
5et-butyl, girt-butyl, dipentyl, 1 isopesityl, girt-butyl, 2-methylbutyl)
Examples include -h+sil-1iso-h+sil-12-ethylbutyl.

As the alkyl group having a substituent,
Examples include Amitsubu D pill, N-(2-aminoethyl)8-aminobu Ojiru, Glycidoshibu Ojiru, Mercaratop D pill, and the like.

The shifter group represented by R1 has 3 to 3 carbon atoms;
It is possible to list 8's Schiff 0 al + Lua k, specifically, Schif 0 p 0 j ru 1 sik 0 butyl ＼ sik O pentyl 1 cyclo he sil cycloheptyl h sik O octyl)
Examples include 3,4-Epogyu Shishiku 0 to Jushir.

R (The alkenyl group shown can include a straight chain or branched alkenyl group having 2 to 4 carbon atoms, and specifically, vinyl, allyl, isopropenyl, 2-
An example is butenyl group.

Examples of the aryl group represented by R1 include a phenyl group, a tolyl group, and a +silyl group. Examples of the aryl group having a substituent include .l-OOphenyl and the like.

Further, in the compound of general formula (4), the ar+r group represented by R2 can be the same as the ar+r group represented by R in the compound of general formula (1).

Specifically, the silane + disilane represented by the general formula (3) includes tetrapyrosilisilicate) methyl (trisyl silane) silane, 5-methyl (; human 0 silane), trimethyl (silane), Silane, ethyl (trihydro) silane, diethyl (dihydro+silane) silane, triethyl (silane) silane, propyl (trihydrosilane)
Silane
Beef Shi) Silane 1 OOpu 0 Bill (Trihydro Beef Shi) Silane, Trifluoro Opu O Hill (Trihydro + Shi) Shira: /
) Aminopropyl (trihydrocarbon) silane, dipropyl (trihydro+silane) silane, methacrylic acid cyprodyl (trihydrohydrogen) silane, and the like. As the silane compound of general formula (4), tetramethodisilane 1 tetraethydisilane) tetrabutydisilane 1 tetrabutydisilane 1 methyl (trimethydisilane)
Silane, dimethyl (shed + silane) silane, trimethyl (
Etogyushi) silane 1 (trimethoxysilane) silane, phenyl (trimethoxysilane) silania) chloropropyl (trimethoxysilane) \trifluoropropylmethoxydisilane, trifluoropropylmethoxydisilane, trifluoropropylmethoxydisilane, glycidyl dipropyl Examples include (trimeth+silane)silane 13,4-epoxycyclohecosilp O-pil (trimethoxysilane)silane, and the like.

The silane compound of general formula (3) can be used as it is, but the silane compound of general formula (4) needs to be used as a hydrolyzate. The hydrolysis method is not particularly limited, and generally known methods can be employed.

For example, neutral water or water made acidic by adding hydrochloric acid may be added to perform hydrolysis at room temperature. The silane compound of general formula (4) may not be completely hydrolyzed, or may be only partially hydrolyzed. Moreover, a part of the compound of the general formula (4) may be partially condensed due to hydrolysis, but it can be suitably used even in such a state.

The organic silane compound containing a silane group of general formula (2) and the silane compound of general formula (4) may be hydrolyzed separately and then mixed, or they may be mixed and then hydrolyzed simultaneously. Also good.

In the coating FA product of the present invention, it is necessary to use the above-mentioned component and component (8) together as the coating film forming component. D
+ 5 to 80% by weight of disilane and/or Shidoro + Shi group-containing organic Shirasashi compound of general formula (2), @component of General formula (3)
) and/or the silane compound of general formula (4) are used in a ratio of 20 to 95% by weight, preferably the former is used in a ratio of 10 to 50% by weight, and the latter is used in a ratio of 50 to 90% by weight. . When the two are combined as a coating film-forming component in this way, a film with good transparency and excellent scratch resistance and antistatic properties is formed. Furthermore, the durability of the abrasion resistance and antistatic properties is also excellent. Furthermore, durability against heat, water, etc. is also improved. If the above-mentioned carrier component is less than 5% by weight, the antistatic performance of the coating film will be insufficient, while if it exceeds 80% by weight, the scratch resistance of the coating film will be insufficient and the water resistance will also be poor.

The coating composition of the present invention can be cured by heating and form a film simply by blending the above components (4) and (8). However, if the synthetic resin has low heat resistance or If the dimensional stability deteriorates, it is preferable to add a curing agent and to effect curing at a low temperature. Even if the synthetic resin has sufficient heat resistance, the rate of film formation can be improved by adding a curing agent. Examples of these curing agents include anthinium perchlorate, perchloric acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its complex with an electron donor, 5nCJ a , Zs
CJ 3, FtC13, AlCl3.5bC1,,T
Lewis acids and their complexes such as ICJ a, organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate, metal borofluorides such as zinc borofluoride and tin borofluoride, boron Boric acid organic esters such as ethyl acid and methyl borate, alkalis such as sodium hydroxide and potassium hydroxide, titanate esters such as tetrabutyrocytitanium, tetraisoprobo+cytitanium, 1g0m acetylacetonate, titanyl acetyl Metal acetylacetonates such as acetonate, aluminum acetylacetonate, cobalt acetylacetonate-nickel acetylacetonate,
N-butylamine tri-n-
Examples include amines such as butylamine, tanidine, cyanide, and isantazyl. Among these curing agents, amine curing agents such as tri-n-butylamine are particularly preferred.

The amount of curing agent used varies depending on the type of curing agent, drying temperature, time, etc., but it is 0.0% based on the entire composition.
Approximately 1 to 10%, more preferably 0.05%
It is about 5%.

Furthermore, the coating composition of the present invention is usually diluted to a concentration suitable for application before use. Examples of the solvent used include alcohols, ketones-ethers, tosolps, esters, halides, carboxylic acids, aromatic compounds, aliphatic hydrocarbons, etc., and these may be used alone or in combination. It can be used as a mixture of two or more types. Particularly preferred among these solvents are methanol, 1 ethanol, n-propanol, isopropanol, tantanol, zze-butanol, and 1zr.
Lower alcohols such as 1-butanol, methylse-O-solp, ethylce-D-solp) butyl-t.

A type of esters such as sorp, lower carboxylic acids such as citric acid, acetic acid, prodionic acid, butyric acid, aromatic compounds such as toluene, silene, etc., and esters such as ethyl acetate, butyl acetate, etc. Or a mixture of two or more.

Furthermore, a leveling agent can be added to the coating composition of the present invention, if necessary, in order to improve the coefficient of friction of the coating surface. As a leveling agent, commercially available
For example, fluorine thread surfactant such as FC-481 (trade name) manufactured by Sumitomo 3M, S
A silicone surfactant such as It-2B (trade name) can be used. A small amount of these leveling agents is sufficient, and 0.0 to the entire composition.
It may be about 1 to 5 times ffi%.

In addition, in the tainter composition of the present invention, deterioration inhibitors such as ultraviolet absorbers and antioxidants, colorants such as pigments and dyes, al, l:f diyl, taraphite, glass fiber, carbon fiber, etc. The inclusion of fillers is optional.

The coating composition of the present invention includes, for example, 1 part acrylic resin, 1 part styrene resin, polycarbonate, 1 part polyester.
It can be applied to molded products and films made of various resins such as vinyl chloride resin and ABS resin.

The coating agent of the present invention can be applied directly onto these resins, but if it is difficult to adhere, apply the coating composition of the present invention after applying an acrylic resin or urethane resin as a primer according to a conventional method. A coating film with excellent adhesion can be obtained by applying a substance.

The coating composition of the present invention can be applied by brushing, spraying, O
-A coating layer can be formed by coating the surface of a synthetic resin with a known method such as a coater or dip coating, and then curing it.Also, a coating composition can be applied to a mold such as S glass or stainless steel by the various methods mentioned above. After applying the material and drying it, there is a method of injecting heated and molten resin, or a method of combining it under heating [i! 2. A method of transferring the coating composition when molding the resin can also be adopted.

As a method for curing the coating composition, various conventional methods such as a method using hot air can be employed, and in general, the coating composition may be cured for about 1 minute to 5 hours at a temperature below the softening temperature of the coated material.

The thickness of the coating film may be appropriately selected depending on the purpose of use of the material to be coated, and generally, if it is about 1 to 10 μm, a scratch-resistant film having sufficient antistatic properties can be obtained.

Effects of the Invention The film formed by the coach ink composition of the present invention is a transparent film that is excellent in both scratch resistance and antistatic properties, and also has excellent scratch resistance and long-lasting antistatic properties. In addition to being a material, it also has good durability against heat, water, etc. The coating composition of the present invention is extremely useful as a protective film for various synthetic resins, such as for electronic equipment, automobile parts,
It has excellent practicality as a coating for building materials, eyeglass lenses, etc.

The present 3VN light will be explained in more detail by showing Examples and Comparative Examples below.

Example 1 50% methanol solution of Shido-Oshibu-O and Rutrimetoshi-disilane (AY-48-024 manufactured by Toshi Silicone Co., Ltd.)
) and 100 parts by weight of methyltriethyldisilane were mixed and cooled to 20"C. Then, 4 parts of 1N hydrochloric acid solution was added
After gradually adding 0 parts over 1 hour, the mixture was aged in a bottle at 2°C to 80'C for hydrolysis.

To this, 3 parts by weight of acetic acid, 22 parts by weight of butyl to sorp, silicone surfactant (S tt manufactured by Toray Silicone)
-28) 0.5 parts by weight, 1.8-Diazazi Schiff 01:
A coating composition was prepared by adding 70.5 parts by weight of 5.4°0] undecene. The obtained coating composition had a solid content concentration of 24% by weight and a viscosity of 5 cmvoice (20% by weight).
It was a colorless and transparent liquid at a temperature of 1.5 °C. This coating composition was applied to an extruded methacrylic resin board by dip coating, and then dried at 80"C for 2 hours. The coated methacrylic resin board was colorless and transparent, and was scratch-resistant by the method shown below. and antistatic properties were measured.

Using o#J abrasive taper abrasion tester (manufactured by Yasuda Seiki), wear wheel C
The coating surface was scratched under the conditions of 3-IQF and a load of 5001, 100 + cycles, and the light transmittance was measured using a hememeter to determine the solder value.

The smaller the haze value, the better the scratch resistance.00 Antistatic property Antistatic property is expressed by the value of the half-life of the charge measured under the following conditions.

After holding the sample for 24 hours under constant temperature and humidity at a temperature of 20"C1 and a relative humidity of 50%, !iE of 10KV was applied for 10 seconds using an Honest meter (manufactured by Shishido Shokai), and the time in the trench until the voltage decreased by half was determined. The half-life was determined by measuring the half-life.The shorter the half-life, the better the antistatic property.

As a result of the above test, the haze value of the coach-inked methacrylic resin plate was 4, the half-life of voltage was 8 seconds, and both scratch resistance and antistatic properties were excellent. Further, there was no change in appearance or physical properties even after the coated article was left at 70'C for 1000 hours and at 50'C and 95% humidity for 1000 hours.

Incidentally, when an untreated methacrylic resin board was similarly tested for scratch resistance and antistatic properties, the valence of 0 was 25 and the half-life of voltage was 120 seconds or more.

Example 2 10 parts by weight of a 50% methanol solution of Shidoro + Sibu O pyrutrimethodisilane and 90 parts by weight of vinyltriethyl disilane (manufactured by Shin-Etsu Chemical Co., Ltd./(BE-1003)),
A coating composition was prepared using components other than the resin in the same proportions as in Example 1. This coating composition was applied to an injection molded polycarbonate resin plate by dip coating, and then dried at 120°C for 2 hours. Coach Inn
) - The polycarbonate resin plate obtained was colorless and transparent, had a haze value of 5 according to a taper abrasion test, and a half-life of voltage of 4 seconds (honest meter, IOA'')').

Example 8 Shido O + 60 parts by weight of a 50% methanol solution of Shido O + Shifurohiltrimethishirane, 35 weight parts of Methyltriethyltrimethoxysilane, Tetraethyltriethyldisilane (5i-42 manufactured by Daihe Kagaku Co., Ltd.)
') Mix 5 parts and 11 parts, and the components other than the resin are from Example 1.
Coating compositions were prepared using similar proportions.

This coachinter composition was applied to a biaxially stretched polyester film (Melinex 506, manufactured by ICI Corporation) using Bar Coater Black 8, and then dried at 180° C. for 2 minutes. The coated biaxially oriented polyester film was colorless and transparent, had a haze value of 4 according to a taper abrasion test, and a voltage half-life of 5 seconds.

Comparative Example 1 A coating composition was prepared in the same manner as in Example 1, except that the hydrosilicone disilane was not used (the ratio of other components to the resin content was the same as in Example 1).

Using this coating composition, a film was formed on a methacrylic resin board in the same manner as in Example 1.

The obtained film was colorless and transparent, and had a haze value of 3 in the taper abrasion test, but the half-life of voltage was 120 seconds or more, and its antistatic properties were poor.

Comparative Example 2 A coating composition was prepared in the same manner as in Example 1 except that 95 parts of a 50% methanol solution of Shidoro+Sibu-O-Pyrtrimethodisilane and 5 parts of Methylmeth+Disilane were used as coating film forming components. was prepared (the ratio of other components to the resin content was the same as in Example 1).

Using this coating composition, a film was formed on a methacrylic resin board in the same manner as in Example 1.

The resulting film had a haze value of 25 in the taper abrasion test and was poor in scratch resistance.

(The above) Agent: Eiji Saegusa, Patent Attorney: Shi2,
7.

Claims (1)

[Claims] (1) (A) a) General formula: [HO(CH_2)_n]_
mSi(OH)_4_-_m (in the formula, n is an integer from 1 to 6,
m is an integer of 1 to 3), and/or b) General formula: [HO(CH_2)_n]_mSi(OR
)_4_-_m (in the formula, R represents an alkyl group or acetyl group having 1 to 4 carbon atoms, and n and m are the same as above), and (B) a ) General formula: R^lSi(OH)_4_-_l(
In the formula, R^1 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an alkenyl group, or an aryl group. The alkyl group, cycloalkyl group, alkenyl group and aryl group may have a substituent selected from halogen, amino, glycidyl and mercapto groups. 1 represents an integer of 0 to 3), and/or b) General formula: R^1lSi(OR^2)_4_-_l(
In the formula, R^2 represents an alkyl group having 1 to 4 carbon atoms or an acetyl group, and R^1 and l are the same as above). and [HO(C
H_2)_n]_mSi(OH)_4_-_m and/or [HO(CH_2)_n]_mSi(OR)_4_-
_m5~80% by weight, R^1lSi(OH)_4_-_
l and/or R^1lSi (OR^2)_4_-_l2
A silane-based coating composition characterized in that the content is 0 to 95% by weight.