JP5395711B2 - Decorative laminated glass - Google Patents

Description

   The present invention relates to a decorative laminated glass obtained by laminating a plate glass, which is inkjet-printed on a plate glass, with a primer layer through contact with an intermediate film.

  Laminated glass is made of a tough resin so that two or more glasses are made in order to minimize injury and accidents caused by glass damage when a person hits the glass or in the unlikely event that the glass breaks due to an earthquake or typhoon. As a highly safe glass that is bonded by thermocompression bonding with an intermediate film, it is widely used for windows, doors, top lights, glass handrails and the like that require safety.

Laminated glass is often colorless and transparent, but in order to impart function and designability, a milky white interlayer is used, or by various printing methods, glass, film, or interlayer film is used. There is decorative glass that prints patterns and patterns, and combines them into glass.

For example, there has been proposed a laminated glass in which decorativeness is imparted to a plate glass or an intermediate film used for laminated glass by various printing techniques such as gravure printing, screen printing, and inkjet printing. (Patent Document 1)
Moreover, the laminated glass which provided the designability by pinching | interposing the resin film which gave the gravure printing and the screen printing inside the laminated glass is proposed. (Patent Document 2)

JP-A-7-309643 JP-A-8-157239

    However, in the laminated glass of Patent Document 1, when the laminated glass is formed, depending on the decorative pattern (when it is not full-surface printing), the site where the printing surface on the printed glass side and the intermediate film are bonded serves as a printing layer and a primer, If the adhesion between the printed layer and the primer is the same as the adhesion between the glass and the interlayer, safety should be ensured if the glass breaks, but if the adhesion is weak, There is a risk that the glass will fall if it is damaged, and if the adhesive force is strong, there is a risk that an object or a person will hit the glass and be injured by penetrating the glass.

    Further, in the laminated glass of Patent Document 2, a synthetic resin intermediate film having an adhesive function is arranged on both sides of the patterned film, and a glass plate is laminated and bonded on both sides of the synthetic resin adhesive layer. The two sheets of glass are bonded to the synthetic resin adhesive layer, and the adhesive strength between the glass and the synthetic resin adhesive layer is maintained, but the pattern layer of the patterned film or the adhesive force between the film and the synthetic resin adhesive layer There was a problem similar to that of Patent Document 1.

   In general, ultraviolet curable inks for inkjet printing have poor adhesion compatibility with glass or resinous intermediate films, and the ink tends to be peeled off from both glass and resinous intermediate films. Therefore, if the decorative laminated glass breaks, there is a risk of peeling between the glass and the inkjet ink, or between the resin intermediate film and the inkjet ink, and the broken glass may collapse. is there.

    On the other hand, if the adhesive force between the glass and inkjet ink or between the resin intermediate film and inkjet ink is too strong, the laminated glass behaves like a single glass, and objects and people collide with the glass. If you do, there is a risk of injury through the glass, which is also a safety issue.

    Therefore, in order to solve the above problems, an object of the present invention is to provide a decorative laminated glass having safety at the time of glass breakage to the same extent as that of ordinary laminated glass, regardless of the print pattern.

   Therefore, in order to improve the safety of decorative laminated glass, the ink-jet printed pattern layer has a primer layer that has moderate adhesion between the glass and the pattern layer, and the adhesion between the pattern layer and the resin intermediate film. It was solved by adopting a structure in which both layers are sandwiched between appropriate adhesive layers.

  The present invention is a decorative laminated glass for solving the above-mentioned problem, and is a laminated glass obtained by laminating at least two plate glasses with an intermediate film made of a resin intermediate film, etc. The plate glass has a pattern layer formed by ink jet printing using an ultraviolet curable resin ink, and has a primer layer between the pattern layer and the plate glass, and further, the pattern layer and the intermediate film A decorative laminated glass characterized by having an adhesive layer made of polyvinyl acetal resin or polyvinyl butyral resin.

  The decorative layered glass pattern layer can be printed in any pattern by sandwiching the primer layer with appropriate adhesion between the glass and the pattern layer and the adhesive layer with appropriate adhesion between the pattern layer and the resin interlayer. Even so, it is possible to maintain safety when the glass is broken. In particular, when the size of the laminated glass is increased, safety aspects such as broken glass become important, and therefore it is important to sandwich the laminated glass with an adhesive layer having appropriate adhesiveness.

  Furthermore, the present invention is a decorative laminated glass characterized in that a hydroxyl group concentration in a polyvinyl acetal resin as an adhesive layer is 20 mol% or more and 40 mol% or less.

  The glass and the resin intermediate film are bonded by hydrogen bonding. In the resin intermediate film used for the laminated glass, the hydroxyl group concentration of the resin intermediate film is optimized in order to maintain an appropriate adhesive force between the glass and the resin intermediate film. That is, it is important to control the hydroxyl group concentration of the adhesive layer in order to obtain an appropriate adhesive force between the glass-adhesive layer and the adhesive layer-resin intermediate film.

  If the hydroxyl group concentration in the polyvinyl acetal resin as the adhesive layer is less than 22 mol%, the adhesive strength is weak, and the glass piece may fall off when the glass is broken. Conversely, if the hydroxyl group concentration in the polyvinyl acetal resin as the adhesive layer exceeds 35 mol%, the adhesive strength is too strong, and the penetration resistance and impact resistance may be lowered. Therefore, the hydroxyl group concentration is 22 mol%. As mentioned above, it is especially preferable to set it as 35 mol% or less.

    According to the present invention, it is possible to supply a decorative laminated glass having safety at the time of glass breakage to the same extent as that of a normal laminated glass regardless of the printed pattern.

It is sectional drawing of the decorative laminated glass of this invention.

(Decorated laminated glass)
FIG. 1 is a cross-sectional view of a decorative laminated glass of the present invention.

    The decorative laminated glass of the present invention is a laminated glass obtained by laminating at least two or more plate glasses 1 with an intermediate film 5 made of polyvinyl butyral resin or the like, and at least one plate glass contains an ultraviolet curable resin ink. The pattern layer 3 is formed by the ink jet printing used, and has a primer layer 2 between the pattern layer and the glass, and an adhesive layer 4 made of polyvinyl acetal resin between the pattern layer and the intermediate film. Consists of.

    The decorative laminated glass can be used for, for example, advertising billboards, guide plates, design partition plates, design handrail plates, architectural design glass panels, vehicle design glass panels, furniture decorative panels, home appliance decorative panels, and the like.

(Base material)
The said base material is plate glass, For example, soda-lime silicate glass or another plate glass is employ | adopted.

(Inkjet printing)
In the ink jet printing of the present invention, a known ink jet printer capable of high-speed printing with high image quality is used. For example, the configuration disclosed in Japanese Patent Application Laid-Open No. 2005-34995 may be used, and for example, a full color on-demand inkjet printer manufactured by Mimaki Engineering (model number JF1631) may be used.

(UV curable resin ink)
In the present invention, an ultraviolet curable resin ink is used for ink jet printing. Examples of the ultraviolet curable resin ink include acrylic resins, polyvinyl resins, polymaleic acid resins, polyester resins, polyether resins, polyurethane resins, polyamide resins, polyepoxy resins, and radiation curing. Any one of resins selected from any of the polymerizable oligomers and monomers can be used, and a mixture of two or more of the above oligomers or monomers can be used.

   The pigment contained in the ultraviolet curable resin ink is an inkjet pigment, and organic pigments other than carbon black and titanium oxide are used. For example, a known organic pigment having excellent weather resistance can be selected.

    For example, in the case of blue, copper phthalocyanine (Pigment Blue 15), metal phthalocyanine, induslen blue (Pigment Blue 22), and bat blue 4, 6, 20 are desirable. In the case of green, pigment green 1, 2, 7, 10, 12, 36, 37, 38, bat green 1, and ingrain green 3 are desirable. In the case of purple, dioxazine violet, pigment violet 19, pigment violet 122, pigment violet 1, pigment violet 2, pigment violet 3, pigment violet 5, bat violet 1, bat violet 3, and bat violet 10 are desirable.

    Further, an activator may be added to the ultraviolet curable resin ink. As the activator, a known surfactant is employed. For example, there are ionic (cationic, anionic, twin) or nonionic (nonionic), and nonionic (nonionic) is particularly desirable. Specific examples include polyethylene glycol monoalkyl ethers or esters and polyethylene glycol alkylphenyl ethers.

(Picture layer)
The pattern of the pattern layer can be arbitrarily set, and characters, geometric patterns, photographs, map information, wood grain patterns, marble patterns, abstract patterns, and the like can be selected.

(Adhesive layer)
For the adhesive layer according to the present invention, a known polyvinyl butyral resin or polyvinyl acetal resin may be employed. For example, Sleksui B (trade name) or Srec K manufactured by Sekisui Chemical Co., Ltd. can be mentioned. In order to ensure safety when the glass is broken, the adhesive strength between the pattern layer or primer layer and the adhesive layer, adhesion Adhesive strength between the layer and the resin intermediate film must be moderately developed. For this purpose, the hydroxyl group concentration of the polyvinyl butyral resin or polyvinyl acetal resin is desirably 20 mol% or more and 40 mol% or less. Specific varieties of ESREC B satisfying the hydroxyl group concentration include BL-1, BL-2, BL-5, BL-10, BL-S, BM-1, BM-2, BM-5, BM- S, BH-3, BH-6, BH-S, BX-1, BX-5, KS-10, KS-1, etc. are mentioned.

(Application method of adhesive layer)
The method for applying the adhesive layer is not particularly limited as long as it is a general wet application method using the resin that becomes the above-mentioned adhesive layer. For example, the adhesive layer is adjusted to a predetermined viscosity, and a roll coater, a flow coater, etc. The method of apply | coating, the method of apply | coating a coating solution with a spray, etc. (refer below Examples 1-6) are mentioned.

  The “viscosity” referred to here is JISK5 6 0 0-2-2 1999 Ford Cup No. 4 The viscosity (unit: second or mPa · s) of a coating solution (room temperature, 25 ° C.) that becomes an adhesive layer was measured using a method, and the coating solution was used as a fixed volume Ford cup N o. 4 is measured by filling a certain amount, flowing down from a hole having a constant diameter, and measuring the flowing time.

  The viscosity condition of the coating solution is particularly preferably 30 to 50 seconds (111 to 185 mPa · s). The thickness of the coating amount is particularly preferably 20 to 25 μm.

(Primer layer)
For the primer layer according to the present invention, a silicone acrylic resin having good adhesion to a metal material, an inorganic material, a glass material, or the like can be used. By using the silicone acrylic resin, the long-term durability of the silicone acrylic resin is also obtained, and it adheres firmly to each material by simple degreasing without pre-treatment, and exhibits sufficient performance. In addition, the work efficiency is good because it is quick drying.

(Resin interlayer)
As the resin intermediate film according to the present invention, a polyvinyl butyral resin (PVB), ethylene vinyl acetate (EVA), or an intermediate film formed by laminating a transparent resin having different physical properties such as viscosity by changing a chemical composition is used. May be.

  Hereinafter, examples of the decorative laminated glass will be further described. The safety of the laminated glass of the present invention was evaluated according to the falling ball test and the shotback test defined in JIS-R3205-2005.

[Example 1]
On a plate glass as a substrate, a glass primer (a soda lime silicate glass primer composed of a silicone acrylic paint) is applied by spraying to a dry coating thickness of 15 to 25 μm at 60 ° C. After drying for 1 hour, an ultraviolet curable resin ink was directly printed on the surface with an inkjet printer (inkjet printing) to form a picture layer. Further, the pattern layer was cured by irradiating the pattern layer with ultraviolet rays by an irradiation device mounted on an ink jet printer.

    For the plate glass, an evaluation sample for a falling ball test has a length of 610 mm, a width of 610 mm, and a thickness of 3 mm, and an evaluation sample for a shotback test has a length of 1930 mm, a width of 864 mm, and a thickness of 3 mm. A thing was used.

    Next, on the pattern layer, polyvinyl butyral resin (S-REC B type: BL-S hydroxyl group concentration 22 mol%), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cellosolve acetate were mixed at a weight ratio of 1: 1: 1. The resulting solution was dissolved in a liquid to a concentration of 10% to obtain a coating solution for spraying. The viscosity is 10 to 15 seconds (37 to 55.5 mPa · s, 25 ° C.) in Ford Cup # 4.

  This coating solution was applied to the inkjet printing surface by spraying so that the dry film thickness was 15 to 20 μm. After coating, the coating was dried at 60 ° C. for 1 hour to obtain a coating film (adhesive layer 4).

  By the manufacturing method described above, the plate glass 1, the primer layer 2 formed on the plate glass 1, the pattern layer 3 formed on the primer layer 2, and the adhesive layer 4 formed on the pattern layer 3 A decorative glass having was obtained.

  Furthermore, the decorative glass, an interlayer film made of polyvinyl butyral resin (thickness of 30 mil was used) and another sheet glass (thickness of 3 mm same as that of the decorative glass) were laminated, The decorative laminated glass shown in FIG. 1 was obtained by thermocompression bonding in an autoclave furnace.

    Then, the safety of the decorative laminated glass was evaluated by the falling ball test and the shotback test defined in JIS R 3205-2005. In addition, in order to confirm the crushing situation at the time of the breakage of the two glasses that make up the laminated glass, in the shotback test, the type III test that continues the test until the two glasses that make up the laminated glass are broken is conducted. did.

(Falling ball test)
A flat decorative laminated glass having a width of 610 mm and a length of 610 mm square was used as a specimen for the falling ball test. The specimen was held in a thermostatic chamber maintained at 23 ° C. for 4 hours, and then a falling ball test was performed. Steel ball, mass among the ² _1/2 of the steel ball calls specified in JIS B 1501 is used as a 1044 g. The test was carried out with 6 specimens.

    The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens were tested without interlayer film cutting, exposure due to missing glass, and peeling of the glass and interlayer film. passed it.

(Shotback test)
The test piece for the falling ball test was a flat decorative laminated glass having a width of 864 mm and a length of 1930 mm square, and the test piece was subjected to a shotback test after being held in a laboratory maintained at 23 ± 5 ° C. for 4 hours or more. . Insert a bolt into the center of the leather bag and stuff it with lead shots, then tighten the top and bottom of the bag with bolts, and diagonally so that the surface of the leather bag overlaps with glass fiber reinforced adhesive tape. And the surface was completely covered, and the mass was 45 kg. The test was carried out with 4 specimens.

    The four specimens were destroyed at the height of the impactor of 30 to 36 cm, and the two glasses constituting the laminated glass were broken. There was no film peeling and the test passed.

[Example 2]
The polyvinyl butyral resin type of the adhesive layer was changed to Seksui Chemical Industry's ESREC B BM-1 (hydroxyl concentration 34 mol%), and the viscosity was changed to 30 to 40 seconds (111 to 148 mPa · s, Ford Cup # 4). Paint the adjusted material with a roll coater. Otherwise, a decorative laminated glass was produced under the same conditions as in Example 1, and a falling ball test and a shotback test were performed.

(Falling ball test)
All six specimens were destroyed at a drop height of 1.2 to 2.4 m, and all six specimens were tested without interlayer film cutting, exposure due to missing glass, and peeling of glass and interlayer film. passed it.

(Shotback test)
The four specimens were destroyed at the height of the impactor of 30 to 36 cm, and the two glasses constituting the laminated glass were broken. There was no film peeling and the test passed.

[Example 3]
Flow coater by changing the type of polyvinyl butyral resin of the adhesive layer to BL-10 (hydroxyl concentration 28 mol%) of S-REC B manufactured by Sekisui Chemical Co., Ltd. and adjusting the viscosity to 40-50 seconds (148-185 mPa · s) Apply with. A decorative laminated glass was produced under the same conditions as in Example 1 except that the coating amount was 20 to 25 μm, and a falling ball test and a shotback test were performed.

(Falling ball test)
The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens were tested without interlayer film cutting, exposure due to missing glass, and peeling of the glass and interlayer film. passed it.

(Shotback test)
The four specimens were destroyed at the height of the impactor of 30 cm, and the two glasses constituting the laminated glass were broken, and when the four specimens were broken, the opening (cut) of the intermediate film, the glass and the intermediate film There was no peeling and the test passed.

[Example 4]
A decorative laminated glass was prepared under the same conditions as in Example 1 except that the polyvinyl butyral resin type of the adhesive layer was changed to the eslek BL-1 (hydroxyl concentration 36 mol%) of the polyvinyl acetal resin, and the falling ball test and the shotback test were performed. Carried out.

(Falling ball test)
The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens passed the test without exposure due to intermediate film cutting or missing glass, but the steel balls dropped. In the vicinity, a slight peeling (about 5 to 10 cm ² ) was observed between the glass and the interlayer film.

(Shotback test)
The four specimens were destroyed at the height of the impactor of 30 to 36 cm, and the two glasses constituting the laminated glass were broken. There was no peeling of the film, and the test was passed, but slight peeling (about 10 to 14 cm ² ) was observed between the glass and the intermediate film in the vicinity of the break starting point of the glass.

    Although the result of the present Example was a little inferior to Safety compared with Examples 1-3, it is the range considered to be satisfactory practically.

[Example 5]
Other than changing the varieties of polyvinyl butyral resin of the adhesive layer to eslec BL-5 (hydroxyl concentration 21 mol%) of polyvinyl acetal resin, adjusting the viscosity to 30 to 40 seconds (111 to 148 mPa · s), and applying a roll coater Produced a decorative laminated glass under the same conditions as in Example 1, and then conducted a falling ball test and a shotback test.

(Falling ball test)
All six specimens were destroyed at a drop height of 1.2 to 2.4 m, and all six specimens passed the test without exposure due to interlayer film cutting or missing glass at the time of destruction, but the steel balls dropped. In the vicinity, a slight peeling (about 10 to 15 cm ² ) was observed between the glass and the interlayer film.

(Shotback test)
The four specimens were destroyed at the height of the impactor of 30 to 36 cm, and the two glasses constituting the laminated glass were broken. Although there was no film peeling, the test was passed, but slight peeling (about 14 to 22 cm ² ) was observed between the glass and the intermediate film in the vicinity of the starting point of breakage of the glass.

   Although the result of the present Example was a little inferior to Safety compared with Examples 1-3, it is the range considered to be satisfactory practically.

[Example 6]
The resin intermediate film is changed from polyvinyl butyral resin to Bridgestone-made ethylene vinyl acetate (EVA) resin, product name EVASAFE, and the viscosity is adjusted to 40 to 50 seconds (148 to 185 mPa · s), and the coating amount is adjusted to 20 to 25 μm. Then, decorative laminated glass was produced under the same conditions as in Example 1 except that the flow coater was applied, and a falling ball test and a shotback test were performed.

(Falling ball test)
The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens were tested without interlayer film cutting, exposure due to missing glass, and peeling of the glass and interlayer film. passed it.

(Shotback test)
The four specimens were destroyed at the height of the impactor of 30 to 36 cm, and the two glasses constituting the laminated glass were broken. There was no film peeling and the test passed.

[Comparative Example 1]
A decorative laminated glass is produced under the same conditions as in Example 1 except that the material of the adhesive layer is changed from polyvinyl butyral resin to urethane resin (Naturo's weather resistant paint Gameron), and a falling ball test and a shotback test are performed. did.

(Falling ball test)
All six specimens were destroyed at a drop height of 1.2 to 2.4 m, and all six specimens passed the test without exposure due to interlayer film cutting or missing glass at the time of destruction, but the steel balls dropped. Peeling was observed between the glass and the interlayer film in a wide range of the laminated glass (about 900-1500 cm ² ), mainly in the vicinity.

(Shotback test)
The four specimens were broken at the height of the impactor of 30 to 48 cm with the two glasses constituting the laminated glass, and when the four specimens were broken, the opening (cut) of the intermediate film or between the glass and the middle There was no peeling of the film, and the test was passed, but peeling occurred between the glass and the interlayer film over a wide range (about 3000 to 6000 cm ² ) centering on the falling glass of some glass pieces and the vicinity of the break starting point of the glass. Observed. The place where peeling occurred between the glass and the interlayer film was a situation where only a small part of the glass fragments was adhered to the interlayer film, and it would not be a problem when dropped.

The result of this comparative example is much inferior in terms of safety compared to Examples 1 to 5, and is very problematic in practical use. (It is highly possible that shattered pieces will fall when the glass breaks.)
[Comparative Example 2]
A decorative laminated glass was prepared under the same conditions as in Example 1 except that the material of the adhesive layer was changed from polyvinyl butyral resin to silicone resin (alco SP of weather resistant paint manufactured by NATCO), and the falling ball test and the shotback test were performed. Carried out.

(Falling ball test)
The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens passed the test without exposure due to intermediate film cutting or missing glass, but the steel balls dropped. Peeling was observed between the glass and the intermediate film in a wide range of the laminated glass (about 1000 to 1500 cm ² ) centering around the vicinity.

(Shotback test)
The four specimens were broken at the height of the impactor of 30 to 48 cm with the two glasses constituting the laminated glass, and when the four specimens were broken, the opening (cut) of the intermediate film or between the glass and the middle There was no peeling of the film, but the test passed, but peeling occurred between the glass and the interlayer film over a wide range (around 5000-7500 cm ² ) centering around the falling glass of some glass pieces and the glass break start point. Observed. The place where peeling occurred between the glass and the interlayer film was a situation where only a small part of the glass fragments was adhered to the interlayer film, and it would not be a problem when dropped.

The result of this comparative example is much inferior in terms of safety compared to Examples 1 to 5, and is very problematic in practical use. (It is highly possible that shattered pieces will fall when the glass breaks.)
[Comparative Example 3]
A decorative laminated glass was produced under the same conditions as in Example 1 except that the material of the adhesive layer was changed from polyvinyl butyral resin to acrylic resin (Letane PG manufactured by Kansai Paint Co., Ltd.), and a falling ball test and a shotback test were performed.

(Falling ball test)
The six specimens were all destroyed at a drop height of 1.2 to 1.9 m, and all six specimens passed the test without exposure due to intermediate film cutting or missing glass, but the steel balls dropped. Peeling was observed between the glass and the intermediate film in a wide range of the laminated glass (about 2000 to 2500 cm ² ), mainly in the vicinity.

(Shotback test)
The four specimens were broken at the height of the impactor of 30 to 48 cm with the two glasses constituting the laminated glass, and when the four specimens were broken, the opening (cut) of the intermediate film or between the glass and the middle There was no peeling of the film, but the test passed, but peeling was observed between the glass and the interlayer film over a wide range (about 5000 to 10000 cm ² ) centering on the falling glass of some glass pieces and the vicinity of the glass break starting point. Observed. The place where peeling occurred between the glass and the interlayer film was a situation where only a small part of the glass fragments was adhered to the interlayer film, and it would not be a problem when dropped.

The result of this comparative example is much inferior in terms of safety compared to Examples 1 to 5, and is very problematic in practical use. (It is highly possible that shattered pieces will fall when the glass breaks.)
From the results of Examples 1 to 5 and Comparative Examples 1 to 3, in providing decorative laminated glass, it is important to select the adhesive force between the interlayer film and the adhesive layer, in other words, the material of the adhesive layer. .

   For the adhesive layer of the decorative laminated glass of the present invention, polyvinyl butyral resin or polyvinyl acetal resin is suitable, and among these, the hydroxyl group concentration in the polyvinyl butyral resin or polyvinyl acetal resin is 22 mol% or more and 35 mol%. If it is as follows, it is possible to provide the safest decorative laminated glass.

1: Sheet glass 2: Primer 3: Picture 4: Adhesive layer 5: Intermediate film

Claims (2)

A laminated glass obtained by laminating at least two plate glasses with a resinous intermediate film, wherein at least one plate glass has a pattern layer formed by ink jet printing using an ultraviolet curable resin ink, And it has a primer layer between the pattern layer and the plate glass, and further has an adhesive layer made of polyvinyl acetal resin or polyvinyl butyral resin between the pattern layer and the intermediate film. Decorative laminated glass. The decorative laminated glass according to claim 1, wherein a hydroxyl group concentration of the adhesive layer is 20 mol% or more and 40 mol% or less.

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