JP2601717B2 - Glass laminate - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass laminate, and more specifically, various types of glass such as plate glass, bottle glass, tableware or householdware glass, lighting glass, decorative glass, and decorative glass. The present invention relates to a glass laminate having a coating layer having a novel surface property formed on a substrate.

2. Description of the Related Art Conventionally, as for glass products, there have been proposed various types of glass products using frosted glass for decoration and light scattering, and glass laminates having a coating layer formed for the purpose of preventing bottle breakage.

Frosted glass is a glass surface that has been provided with irregular and fine irregularities by applying a matting treatment to the glass surface, giving it a function of preventing luxury and direct transmission of light rays. A physical method of making fine scratches on the glass surface with an abrasive such as sand, or a chemical method of corroding with a matting liquid containing hydrofluoric acid, ammonium fluoride and water as main components is used.

On the other hand, with respect to a glass laminate aimed at preventing bottle breakage, a resin coating layer is often provided on the surface of a glass container.
Nos. 129844 and 57-191254, polyurethane resins as described in JP-A-58-189262, rubber-based coating materials as described in JP-A-58-189262, and JP-A-57-147560. Various types of epoxy resins have been proposed, and a rubber-based coating is provided on the surface of a glass bottle, and an epoxy resin coating is provided thereon. Products coated with electric powder spray and cured by heating have been put to practical use.

Problems to be Solved by the Invention By the way, when a matte glass is obtained by a physical method, the purpose of light scattering is achieved, but a high-grade feeling cannot be obtained due to the rough unevenness, and when obtained by a chemical method, Although a high-class feeling can be obtained, there is a problem that the treatment involves danger and that the disposal of waste liquid for preventing pollution is costly.

On the other hand, when applying a resin coating on the surface of the glass container,
It is effective in preventing glass fragments from being scattered due to breakage, preventing the glass container from being damaged or damaged, etc., but its appearance is not matte, and is not intended to give a sense of quality.

The present invention has been made in view of such a situation in the related art.

Accordingly, an object of the present invention is to provide a glass laminate having a matte surface with a soft feel and a rubber-like elasticity using a resin coating composition.

Means and Action for Solving the Problems The glass laminate having a matte surface according to the present invention comprises: (A) a polyurethane resin having a hydroxyl value of 1 to 50 on a glass substrate;
0 parts by weight, (B) 10 to 100 parts by weight of an inorganic or organic filler, and (C) an isocyanate prepolymer are blended such that the isocyanate group is 0.8 to 5.0 in equivalent ratio to the hydroxyl group of the component (A). A coating layer is formed by the coating composition, and the surface of the coating layer has a pitch of 0.1 to 50 μm, preferably 0.5 to 30 μm, particularly preferably 1.0 to 15 μm, and a depth of 0.1 to 25 μm, preferably 0.5 to 15 μm. With irregularities,
The 60-degree light reflectance is 0.1-20%, preferably 0.2-10%,
The surface dynamic friction coefficient is 0.15 to 0.50, preferably 0.2 to 0.4, and the thickness of the coating layer is 3 to 200 μm, preferably 20 to 8
0 μm.

 Hereinafter, the present invention will be described in detail.

FIG. 1 shows an embodiment of the glass laminate of the present invention, wherein 1 is a glass substrate and 2 is a coating layer. The coating layer is in a state in which the filler 4 is dispersed in the resin matrix 3. FIG. 2 shows another embodiment of the glass laminate of the present invention.
Shows the case where was formed.

The surface characteristics of the coating layer specified in the present invention express the texture and appearance of the surface having the design function aimed by the present invention, and are expressed by the following mechanical measurement values.

The pitch and the depth are average values of values obtained by observing the pitch length and the depth of the convex portions of the unevenness formed on the surface of the coating layer by observing the images with an electron micrograph.

The 60-degree light reflectivity is measured by the method of JIS Z8741. The light is applied to the surface of the coating layer at an incident angle of 60 degrees, and the light receiving rate of the reflected light is expressed in%.

The surface dynamic friction coefficient is measured by applying a vertical load of 500 g to a test piece (dimensions: 100 mm x 200 mm) using a surface tester,
It is calculated as a value obtained by reducing the average frictional resistance when moved by 100 mm at 50 mm / min by the vertical load.

The film thickness of the coating film of the coating layer is an average value of values measured by observing a cross section with an electron micrograph.

In the present invention, the pitch and depth of the irregularities on the surface of the coating layer are factors involved in the feel and appearance, and the pitch is 0.
When it is smaller than 1 μm, the slipperiness decreases in the texture,
As for the appearance, the sense of quality is slightly reduced. On the other hand, if it exceeds 50 μm, the soft feeling of the texture is impaired, and the appearance is unfavorably rough. On the other hand, if the depth is less than 0.1 μm, the soft feeling is impaired, while if it exceeds 25 μm, the slip property is undesirably increased.

The 60-degree light reflectance is an element whose appearance looks like frosted glass. If the reflectance is more than 20%, the texture is diminished, which is not preferable.

Further, the surface dynamic friction coefficient is a factor that contributes to the moist feeling of the hand. If the coefficient is less than 0.15, the moist feeling is diminished, while if it exceeds 0.50, the tackiness is undesirably increased.

Further, when the coating layer has a thickness of 3 to 200 μm, the coldness of the glass is reduced, and a warm touch is provided. If the film thickness is less than 3 μm, a warm feel cannot be obtained, while it is practically difficult to obtain a film thickness of 200 μm or more.

Next, the materials constituting the glass laminate of the present invention will be described.

Examples of the glass substrate that can be used in the present invention include plain glass, plate glass such as window glass, beer bottles, Western wine bottles, sake bottles such as sake bottles, drink bottles such as juice and cider, tableware containers such as cups and bowls, and medicinal products. Examples include household goods such as bottles and food containers, lighting glasses such as electric light shades and gloves, crafts, decorative glass such as stained glass, glass buttons, and decorative glass such as artificial pearls.

As a coating composition for forming a coating layer, a hydroxyl value of 1 to 1
A composition having a 100% modulus of 20 to 100 kg / cm ² of a coating film containing 50 polyurethane resins and various fillers and a crosslinking agent is used.If necessary, a coloring agent, an antioxidant,
A crosslinking accelerator may be used. When this is coated, the one whose mixing ratio is determined so as to have the surface properties of the coating layer is used.

The polyurethane resin having a hydroxyl group in the molecule in the component (A) is obtained by reacting a polyol, an organic diisocyanate and a chain extender, and has a hydroxyl value of 1 to 50, preferably 1 to 30. Things are used. When the hydroxyl value is less than 1, the abrasion resistance and durability of the coating film are inferior. On the other hand, when it exceeds 50, drying of the coating film is slow and workability is inferior. Those in the range are preferred.

As the polyol component, those having a molecular weight of 500 to 4000 are used, for example, polyethylene glycol adipate, polyethylene propylene glycol adipate,
Polyethylene butylene glycol adipate, polyethylene glycol adipate, polybutylene glycol adipate, polyethylene glycol succinate, polyethylene glycol sebacate, polybutylene glycol sebacate, polytetramethylene ether glycol, poly-ε-caprolactone diol, polyhexamethylene glycol adipate, polycarbonate Polyol, polymethylpentenediol adipate, polypropylene glycol, polybutadiene glycol, water-added polybutadiene glycol and the like can be used.

Organic diisocyanates include 4,4'-diphenylmethane diisocyanate (MDI), MDI with water, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate (XDI), and water
XDI, 2,4-tolylene isocyanate, 2,6-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate and the like can be used.

As chain extenders, ethylene glycol, 1,2-
Propanediol, 1,3-butanediol, neopentyl glycol, 1,4-butanediol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-bis- (β -Hydroxyethyl) terephthalate, 2,2-bis- (4-β-hydroxyethoxyphenyl), 1,4-cyclohexanediol and the like can be used.

As the inorganic or organic filler of the component (B), a particle size of 0.
Those having 5 to 30 μm are suitable, and as the inorganic filler, precipitated calcium carbonate, light calcium carbonate,
Heavy calcium carbonate, calcium silicate, clay, synthetic silicate, silicate fine powder, etc. can be used, while organic fillers include nylon powder, fluororesin powder, polyurethane beads, polyethylene beads, polypropylene beads, polyethylene -Vinyl acetate copolymer beads, polysiloxane beads, cross-linked polystyrene beads, cross-linked polymethyl methacrylate beads, cross-linked benzoguanamine resin beads and the like can be used.

When the particle size of these filler particles is less than 0.1 μm,
The adhesiveness on the surface of the coating film is increased. On the other hand, if it exceeds 50 μm, the soft feeling of the coating film is lost.

As the isocyanate prepolymer of the component (C),
Trimethylolpropane adduct of tolylene diisocyanate (Sumidur L-75: manufactured by Sumitomo Bayer), trimethylolpropane adduct of xylylene diisocyanate (Takenate D-110N: manufactured by Takeda Pharmaceutical), 1,6-hexamethylene diisocyanate It is suitable to use a reaction product of 1,6-hexamethylene diisocyanate with water (Sumidur N-75: manufactured by Sumitomo Bayer) or the like (trimethylolpropane adduct (Sumidur HT: manufactured by Sumitomo Bayer)).

The value of the 100% modulus of the coating of the coating composition comprising components (A), (B) and (C) of not more than 20 to 100 kg / cm ² is:
It is an indispensable requirement to have a soft touch and a moist feeling. At 20 kg / cm ² or less, stickiness occurs, the moist feeling is weakened, and at 100 kg / cm ² or more, the soft feeling is impaired. A preferred range is 30-50 kg / cm ² . The 100% modulus means the stress when the test piece is given 100% elongation (that is, when it is doubled), and is referred to as "JIS K6301-1-1975 3.4.3 Tensile stress". Measurement ".

The above components (A) to (C) are added to a suitable organic solvent to prepare a coating composition. Examples of the organic solvent to be used include ethyl acetate, butyl acetate, methyl isobutyl ketone, cyclohexanone, and ethyl acetate. Cellosolve acetate, butyl cellosolve acetate, toluene, xylene and the like can be mentioned.

As means for coating the coating composition on a glass substrate, known means such as a spray coating method, a dip coating method, and a casting coating method can be applied. In that case, the coating composition is
Apply so that the dry film thickness is 3-200 μm, and
C., preferably at 100 to 150.degree. C. for 3 to 10 minutes.

Furthermore, in the present invention, in order to improve the adhesion between the glass substrate and the coating layer, it is preferable to provide a subbing layer such as a silane coupling agent, a titanate compound, an epoxy resin and a curing agent which are generally used, They may also be colored.

 Specifically, the following can be exemplified.

Silane coupling agent: N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and the like.

Titanate compounds: isopropyl triisostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2, 2-diallyloxymethyl-1-butyl) bis (didodecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltricumylphenyltitanate, isopropyltri (N-aminoethyl) Aminoethyl) titanate and the like.

Epoxy resin: bisphenol A type epoxy resin, bisphenol F
Epoxy resin, bisphenol AD epoxy resin, bromide-containing epoxy resin, novolak epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, heterocyclic epoxy resin, etc.

Curing agent: aliphatic diamine, aliphatic polyamine, aliphatic polyamine containing aromatic ring, alicyclic polyamine, cyclic polyamine,
Polyaminoazide, dicyandiamide, imidazoles, polymercaptan, isocyanate, blocked isocyanate and the like. The coating of the primer can be carried out by a conventional method such as dip coating, spray coating, cast coating, etc., and usually forms a primer coating film having a thickness of 0.1 to 100 μm.

The glass laminate of the present invention has a surface of the coating layer formed on the glass substrate as described above, the pitch is 0.1 to 50 μm,
It has irregularities with a depth of 0.1 to 25 μm and a light reflectance of 60 degrees of 0.1
20%, the surface dynamic friction coefficient is 0.15 to 0.50, and from the 100% modulus of the coating of the coating layer is 20 and 100 kg / cm ^2, light projected on the surface according to the pitch and depth of the surface irregularities And irregularly reflected, giving the appearance of frosted glass. In addition, when the surface of the coating layer is touched with a finger, the contact area with the finger is reduced, so that the touch layer has a unique texture.

In addition, since the coating layer has a thickness of 3 to 200 μm, the coldness of the glass is reduced, and a warm touch is provided.

Examples Hereinafter, examples of the present invention will be described.

First, specific examples of the coating composition used in the present invention will be described.

Example 1 1,4-butylene glycol adipate (average molecular weight 200
0, hydroxyl value 56) 1000 parts, 902 parts of toluene and 157 parts of toluylene diisocyanate were mixed, reacted at 100 to 110 ° C. for 4 hours, and 45 parts of 1,4-butylene glycol was added.
The reaction was continued for another 2 hours. After confirming that the isocyanate had disappeared, 902 parts of ethyl acetate was added, and the mixture was cooled to room temperature with stirring to obtain a transparent polyurethane solution having a solid content of 40%, a viscosity of 1000 cps / 30 ° C., and a hydroxyl value of 3.7.

Example 2 1000 parts of polytetramethylene glycol (average molecular weight: 1,000, hydroxyl value: 112), 881 parts of toluene and 175 parts of water-added xylylene diisocyanate were mixed and reacted at 100 to 110 ° C. for 4 hours. After confirming that the isocyanate had disappeared, 881 parts of butyl acetate was added, and the mixture was cooled to room temperature with stirring to obtain a transparent polyurethane solution having a solid content of 40%, a viscosity of 350 cps / 30 ° C., and a hydroxyl value of 3.8.

Example 1 After washing a commercially available clear glass bottle of 720 ml with isopropyl alcohol, a silane coupling agent (KBM-60) was used.
3. Shin-Etsu Silicon Co., Ltd.) A mixture of 15 parts by weight and 85 parts by weight of lacquer thinner is spray-coated evenly to a dry film thickness of 5 μm, and heated and dried at 80 ° C. for 20 minutes to form an undercoat layer. Formed.

Next, 0.6 parts by weight of dibutyltin dilaurate (L-101, manufactured by Tokyo Fine Chemical Co., Ltd.) and 180 parts by weight of lacquer thinner were added as catalysts to 100 parts by weight of the polyurethane resin (polyurethane solution of the above Example 1). 20 parts by weight of a silica fine powder (Nipril E-220A, manufactured by Nippon Silica Co., Ltd.) having an average particle diameter of 1 μm is dispersed by a high-speed stirrer, and then an isocyanate prepolymer (Sumidur N-7) is dispersed.
5, (NCO content 16%), manufactured by Sumitomo Bayer Urethane Co., Ltd.)
A coating solution to which 5 parts by weight was added was prepared.

The above coating solution was overcoated on the undercoat layer by spray coating, and then heated and dried at 80 ° C. for 20 minutes to obtain a glass bottle having a coating layer having a thickness of 30 μm.

The surface roughness, 60-degree light reflectance and surface dynamic friction coefficient of the obtained laminated glass bottle were measured. The results are shown in Table 1.

The laminated glass bottle had a peculiar surface property such that the texture had a moist and soft feeling, while the appearance looked like matte glass.

Example 2 A laminated glass bottle was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed to 4 μm in the method of Example 1, and the surface properties, appearance, and texture were similarly evaluated.
The results were as shown in Table 1.

Examples 3 to 5 A laminated glass bottle was obtained in the same manner as in Example 1, except that the particle size of the silica fine powder of the coating composition was changed as shown in Table 1. The surface properties, appearance, and texture of each of the obtained laminated glass bottles were as shown in Table 1.

Examples 6 to 9 A laminated glass bottle was obtained in the same manner as in Example 1, except that the addition amount of the silica fine powder of the coating composition was changed as shown in Table 1. The surface properties, appearance, and texture of each of the obtained laminated glass bottles were as shown in Table 1.

Examples 10 and 11 A commercially available black 720 ml brandy bottle was washed with isopropyl alcohol, and then washed with epoxy resin (Epicoat 10).
07 (Mw = 2900, epoxy equivalent 1750-2100), Yuka Shell Epoxy Co., Ltd.) 75 parts by weight of lacquer thinner 675
Add polyamide resin (Versamide) to the solution
100, manufactured by Henkel Hakusui Co., Ltd.)
The coating was uniformly applied to a thickness of μm and dried by heating at 80 ° C. for 30 minutes to form an undercoat layer.

Next, 0.6 parts by weight of dibutyltin dilaurate and 200 parts by weight of lacquer thinner were added as catalysts to 100 parts by weight of the polyurethane resin (polyurethane solution of Example 2 above), and nylon fine powder having a particle diameter of 10 μm (Orgasol 2002EX-
D, Nippon Rilsan Co., Ltd.) 40 or 80 parts by weight were dispersed with a high-speed stirrer, and then 10 parts by weight of an isocyanate prepolymer (Duranate E-402-90T (NCO content 8.5%), Asahi Kasei Kogyo Co., Ltd.) Was added to prepare a coating solution.

On top of the undercoat layer, the coating solution was spray-coated and then dried by heating at 80 ° C for 30 minutes.
A glass bottle having a coating film of 40 or 60 μm was obtained.
Table 1 shows the results of the evaluation.

Comparative Example 1 A laminated glass bottle was obtained in the same manner as in Example 1 except that the thickness of the coating layer was changed to 2 μm in the method of Example 1, and the surface properties, appearance, and texture were similarly evaluated.
The results are as shown in Table 1, and a warm touch like the laminated glass bottle obtained in the above example was not obtained.

Comparative Examples 2 and 3 A laminated glass bottle was obtained in the same manner as in Example 1, except that the composition of the coating composition was partially changed as shown in Table 1. The surface properties, appearance, and texture of each of the obtained laminated glass bottles are as shown in Table 1, and a unique surface property such as the laminated glass bottle obtained in the above example was not obtained.

Comparative Example 4 A laminated glass bottle was obtained in the same manner as in Example 1, except that the coating thickness of the coating layer was changed to the value shown in Table 1. The surface characteristics, appearance, and texture of each of the obtained laminated glass bottles are as shown in Table 1, and a warm touch like the laminated glass bottle obtained in the above example was not obtained.

Comparative Example 5 In Example 10, except that the composition of the coating composition was partially changed as shown in Table 1, the same method was carried out.
A laminated glass bottle was obtained. The surface properties, appearance, and texture of the obtained laminated glass bottle are as shown in Table 1, and the soft, warm, and slippery feelings like the laminated glass bottle obtained in the above example were not obtained.

Comparative Example 6 The same glass bottle as in Example 1 was washed with isopropyl alcohol, and then immersed in an aqueous solution of 40% ammonium hydrogen fluoride for 3 minutes. After pulling up, it was sufficiently washed to obtain a frosted glass bottle. The surface characteristics, appearance and texture of the obtained bottle were as shown in Table 1.

Effect of the Invention Since the glass laminate of the present invention is provided with the coating layer having the above-mentioned surface characteristics and film thickness, the texture is frosted glass, but the texture is moist and soft, despite the appearance. And warm surface. Therefore, by providing such a coating layer, the texture of the glass substrate is changed, a warm, soft touch is imparted, and a fashion-like composite function having a calm appearance is obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of the glass laminate of the present invention, and FIG. 2 is a cross-sectional view of another embodiment of the glass laminate of the present invention. 1 ... glass substrate, 2 ... coating layer, 3 ... resin matrix, 4 ... filler, 5 ... undercoat layer.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Yoshida 3-133, Hiyoshi-cho, Nagata-ku, Kobe-shi, Hyogo Inside Honey Chemical Co., Ltd. (56) References JP-A-53-140338 (JP, A)

Claims (2)

(57) [Claims] 1. A glass substrate comprising (A) 100 parts by weight of a polyurethane resin having a hydroxyl value of 1 to 50, (B) 10 to 100 parts by weight of an inorganic or organic filler, and (C) an isocyanate prepolymer. A coating layer is formed by a coating composition blended such that the isocyanate group is 0.8 to 5.0 in equivalent ratio to the hydroxyl group of A), and the surface of the coating layer has a pitch of 0.1 to 50 μm and a depth of 0.1 to 50 μm. It has irregularities of 25 μm and 60
Degree of light reflectance is 0.1-20%, surface dynamic friction coefficient is 0.15-0.50
And the 100% modulus of the coating of the coating layer is 20 to 100.
kg / cm ² and a film thickness of 3 to 200 μm. 2. The glass laminate having a matte surface according to claim 1, wherein the glass substrate is a container.