阅读说明：本技术 Pvb膜和夹层玻璃 (PVB film and laminated glass ) 是由 赵悦悦 吴嘉名 冯加晔 于涌 谭诗圻 严册 于 2019-10-28 设计创作，主要内容包括：本发明公开了一种PVB膜,由PVB组合物制备得到,按重量份计,所述PVB组合物包括聚乙烯醇缩丁醛60～90份、交联剂体系1～30份和增塑剂1～40份,所述交联剂体系中包括质量比依次为(30～50):(40～60):(5～10)的苯甲酸或苯甲酸类似物、烷基酚和酸酐。本发明还公开了一种夹层玻璃。(The invention discloses a PVB film which is prepared from a PVB composition, wherein the PVB composition comprises, by weight, 60-90 parts of polyvinyl butyral, 1-30 parts of a cross-linking agent system and 1-40 parts of a plasticizer, and the cross-linking agent system comprises benzoic acid or benzoic acid analogues, alkylphenol and anhydride in a mass ratio of (30-50) to (40-60) to (5-10) in sequence. The invention also discloses the laminated glass.)

1. The PVB film is characterized by being prepared from a PVB composition, wherein the PVB composition comprises 60-90 parts by weight of polyvinyl butyral, 1-30 parts by weight of a cross-linking agent system and 1-40 parts by weight of a plasticizer, and the cross-linking agent system comprises benzoic acid or benzoic acid analogues, alkylphenol and acid anhydride in a mass ratio of (30-50) - (40-60) - (5-10).

2. A PVB film according to claim 1, wherein the mass percentages of said benzoic acid or benzoic acid analog, said alkylphenol, and said anhydride in said crosslinker system are 30% to 50%, 40% to 60%, and 5% to 10%, respectively.

3. A PVB film according to claim 1, wherein the anhydride is selected from one or both of maleic anhydride and phthalic anhydride.

4. A PVB film according to claim 1, wherein the crosslinker system further comprises a diisocyanate.

5. A PVB film according to claim 3, wherein said alkylphenol is selected from one or more of alkyl sulfonate phenol, alkylphenol ethoxylate, propyl phenol, butyl phenol, amyl phenol, heptyl phenol, octyl phenol, nonyl phenol, and decyl phenol.

6. The PVB film of claim 3, wherein the benzoic acid analog is selected from one or more of dioctyl terephthalate and di (2-ethylhexyl) phthalate.

7. A PVB film according to any one of claims 1 to 6, wherein said plasticizer is selected from the group consisting of phosphate and adipate mixtures, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, 1, 2-cyclohexane dicarboxylic acid diisononyl ester, triethylene glycol dicaprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1, 3-propanediol di-2-ethylbutyrate, 1, 4-butanediol di-2-ethylbutyrate, 1, 2-butanediol di-2-ethylbutyrate, One or more of diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylvalerate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, dihexyl adipate, dioctyl adipate, hexyl adipate, diisononyl adipate, heptyl adipate, dibutyl sebacate, oil-modified alkyds, and adipates.

8. A PVB film according to any one of claims 1-6 further comprising from 0.1 to 1 part of an ultraviolet absorber selected from the group consisting of one or more of benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, and hindered amine compounds.

9. A PVB film according to any one of claims 1-6 and 8, further comprising 0.1 to 1 part of an antioxidant selected from the group consisting of 2, 2-bis [ [ [ [ [ [3- (2, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] oxy ] methyl ] propane-1, 3-dioxane ], 2, 6-di-t-butyl-4-methylphenol, 1, 3-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 4 '-thiobis (6-t-butyl-3-methylphenol), 4' -dimethyl-6, 6 '-di (t-butyl) 2,2' -methylenebis (phenol), 2, 6-di-t-butyl-cresol and 4,4' -butylidene bis- (6-tert-butyl) -3-methylphenol.

10. A laminated glass, wherein an interlayer film of the laminated glass comprises the PVB film of any of claims 1-9.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a PVB film and laminated glass.

Background

Due to the excellent durability, safety, reduced sound and weather resistance of laminated glass, it is expected that the demand in construction will expand at an industrial level. Polyvinyl butyral (PVB) film, which can be used in the manufacture of interlayers of laminated glass, is a polymeric material formed by plasticating and extruding PVB with a plasticizer.

Conventional PVB interlayers have poor tear strength and stiffness, and are difficult to withstand heavier loads and stronger impacts. The Konno company chemically modifies PVB resin, and enables the PVB film product to obtain higher mechanical properties through the interaction of intermolecular ionic groups. Furthermore, knoo also designed a PVB film (Saflex DG) in a multilayer structure. The Saflex DG structural interlayer has excellent tensile strength (up to 33MPa), as well as excellent safety after fracture, excellent edge stability and thermal stability compared to conventional PVB (about 20-26 MPa). However, the PVB resin has low modification reaction yield, complex synthetic route and difficult operation, and increases the production cost. Moreover, the superior interlayer strength of Saflex DG results in lower elongation at break, and therefore cannot meet the performance requirements of more demanding laminated glass. CN102417682A utilizes the addition of nano-cellulose and nano-TiO containing rich OH groups in PVB resin₂Firstly, titanium-based alcohol is generated and then reacts with Si-OH on the surface of glass to generate Ti-O-Si bonds, finally a net structure is formed and the mechanical properties of the PVB film are improved, however, the physical properties of the produced PVB film are not ideal, such as tensile strength and elongation at break, and still fall behind the international high-end products. In addition, in order to improve the mechanical properties of the PVB film, US4575540 uses a low-boiling point small molecule such as formaldehyde as a crosslinking agent to increase the molecular weight of the PVB resin, but when the PVB resin is crosslinked, the high activity and low selectivity of the acetal reaction make the crosslinking controllability poor, the resin is easy to agglomerate during synthesis, and the uniformity, haze and light transmittance of the resin particles are greatly influenced. And uneven crosslinking makes part of the resin difficult to plasticize in the extrusion process to generate crystal point defects, and low weight exists in the mass production processThe renaturation and the mechanical property are not uniform, and the like.

Disclosure of Invention

Based on the above, it is necessary to provide a PVB film and laminated glass for solving the problems of easy agglomeration in the synthesis of the conventional PVB film and poor mechanical properties of the prepared PVB film.

The PVB film is prepared from a PVB composition, the PVB composition comprises 60-90 parts by weight of polyvinyl butyral, 1-30 parts by weight of a cross-linking agent system and 1-40 parts by weight of a plasticizer, and the cross-linking agent system comprises benzoic acid or benzoic acid analogues, alkylphenol and anhydride in a mass ratio of (30-50) to (40-60) to (5-10) in sequence.

In one embodiment, the mass percentages of the benzoic acid or benzoic acid analog, the alkylphenol, and the anhydride in the crosslinker system are 30% to 50%, 40% to 60%, and 5% to 10%, respectively.

In one embodiment, the anhydride is selected from one or both of maleic anhydride and phthalic anhydride.

In one embodiment, the crosslinker system further comprises a diisocyanate.

In one embodiment, the alkylphenol is selected from one or more of alkyl sulfonate phenol, alkylphenol ethoxylate, propyl phenol, butyl phenol, amyl phenol, heptyl phenol, octyl phenol, nonyl phenol, and decyl phenol.

In one embodiment, the benzoic acid analog is selected from one or more of dioctyl terephthalate and di (2-ethylhexyl) phthalate.

In one embodiment, the plasticizer is selected from the group consisting of a mixture of phosphate and adipate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, 1, 2-cyclohexanedicarboxylic acid diisononyl ester, triethylene glycol dicaprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1, 3-propanediol di-2-ethylbutyrate, 1, 4-butanediol di-2-ethylbutyrate, 1, 2-butanediol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, and mixtures thereof, Diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylvalerate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol di-caprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, dihexyl adipate, dioctyl adipate, hexyl adipate, diisononyl adipate, heptyl adipate, dibutyl sebacate, oil-modified alkyds, and adipates.

In one embodiment, the PVB composition further comprises 0.1 to 1 part of an ultraviolet absorber.

In one embodiment, the ultraviolet absorber is selected from one or more of a benzotriazole compound, a benzophenone compound, a triazine compound, a benzoate compound, and a hindered amine compound.

In one embodiment, the PVB composition further comprises 0.1 to 1 part of an antioxidant.

In one embodiment, the antioxidant is selected from the group consisting of 2, 2-bis [ [ [ [3- (2, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] oxy ] methyl ] propane-1, 3-dioxane ], 2, 6-di-tert-butyl-4-methylphenol, 1, 3-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 4,4' -thiobis (6-tert-butyl-3-methylphenol), 4' -dimethyl-6, 6' -di (tert-butyl) 2,2' -methylenebis (phenol), 2, 6-di-tert-butyl-cresol and 4,4' -butylidenebis- (6-tert-butyl) -3-methylphenol.

A method of making a PVB film comprising: heating and extruding the PVB composition at 140-150 ℃.

A laminated glass, an intermediate film of the laminated glass comprises the PVB film or the PVB film prepared by the PVB film preparation method.

The PVB film is prepared from the PVB composition, and the acid anhydride in the cross-linking agent system is used for enhancing the cross-linking of the polyvinyl butyral and improving the mechanical strength of the PVB film. The acid anhydride and polyvinyl butyral in the PVB composition are powdery solids that are not easily uniformly dispersed during the manufacturing process, and thus the degree and uniformity of crosslinking cannot be controlled. According to the invention, benzoic acid or benzoic acid analogue and alkylphenol are added into a cross-linking agent system, on one hand, acid anhydride is dissolved in alkylphenol, benzoic acid or benzoic acid analogue solvent, so that the cross-linking agent system solution containing alkylphenol, benzoic acid or benzoic acid analogue solvent can bring the acid anhydride to the periphery of polyvinyl butyral more easily, the effect of uniformly dispersing the polyvinyl butyral and the acid anhydride is achieved, the reaction stability of the acid anhydride and the polyvinyl butyral in the cross-linking process is improved, and the cross-linking degree and uniformity are effectively controlled; on the other hand, by adding alkylphenol, benzoic acid or benzoic acid analogues containing rigid benzene ring structures, the mechanical properties of the PVB film can be obviously enhanced, so that the PVB film can obtain high tensile strength, tearing strength and excellent elongation at break, and simultaneously maintains high transparency to meet the properties of high-standard laminated safety glass.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The embodiment of the invention provides a PVB film, which is prepared from a PVB composition, wherein the PVB composition comprises 60-90 parts by weight of polyvinyl butyral, 1-30 parts by weight of a cross-linking agent system and 1-40 parts by weight of a plasticizer, and the cross-linking agent system comprises benzoic acid or benzoic acid analogues, alkylphenol and acid anhydride in a mass ratio of (30-50) - (40-60) - (5-10).

The PVB film provided by the embodiment of the invention is prepared from the PVB composition, and the acid anhydride in the cross-linking agent system is used for enhancing the cross-linking of the polyvinyl butyral and improving the mechanical strength of the PVB film. The acid anhydride and polyvinyl butyral in the PVB composition are powdery solids that are not easily uniformly dispersed during the manufacturing process, and thus the degree and uniformity of crosslinking cannot be controlled. In the embodiment of the invention, benzoic acid or benzoic acid analogue and alkylphenol are added into a cross-linking agent system, on one hand, acid anhydride is dissolved in alkylphenol, benzoic acid or benzoic acid analogue solvent, so that the cross-linking agent system solution containing alkylphenol, benzoic acid or benzoic acid analogue solvent can bring the acid anhydride around polyvinyl butyral more easily, the effect of uniformly dispersing the polyvinyl butyral and the acid anhydride is achieved, the reaction stability of the acid anhydride and the polyvinyl butyral in the cross-linking process is improved, and the cross-linking degree and uniformity are effectively controlled; on the other hand, by adding alkylphenol, benzoic acid or benzoic acid analogues containing rigid benzene ring structures, the mechanical properties of the PVB film can be obviously enhanced, so that the PVB film can obtain high tensile strength, tearing strength and excellent elongation at break, and simultaneously maintains high transparency to meet the properties of high-standard laminated safety glass.

In one embodiment, the anhydride, the benzoic acid or benzoic acid analog, and the alkylphenol are added to the PVB composition as a whole in a crosslinker system to better achieve uniform dispersion of the anhydride and the polyvinyl butyral. In one embodiment, the mass ratio of the benzoic acid or benzoic acid analog, the alkylphenol, and the acid anhydride can be (30-50): (40-60): (5-10), and the inventors have found through experimental studies that, in this mass ratio range, the acid anhydride has good solubility in the benzoic acid or benzoic acid analog and the alkylphenol, and the cross-linking agent system can be dispersed in the polyvinyl butyral more easily. In one embodiment, the mass percentages of the benzoic acid or benzoic acid analog, the alkylphenol, and the anhydride in the crosslinker system are 30% to 50%, 40% to 60%, and 5% to 10%, respectively. Within this mass fraction range, the acid anhydride and polyvinyl butyral are more crosslinkable, and the mechanical strength of the resulting PVB film is higher.

In one embodiment, the alkylphenol may be selected from one or more of alkyl sulfonate phenol, alkylphenol ethoxylate, propyl phenol, butyl phenol, amyl phenol, heptyl phenol, octyl phenol, nonyl phenol, and decyl phenol.

In one embodiment, the benzoic acid analog may be selected from one or more of dioctyl terephthalate and di (2-ethylhexyl) phthalate.

In one embodiment, the anhydride may be selected from one or both of maleic anhydride and phthalic anhydride.

In an embodiment, the crosslinker system may further comprise a diisocyanate. The mass percentage of the diisocyanate in the crosslinker system may be 2% to 10%. In one embodiment, the plasticizer may be selected from the group consisting of a mixture of phosphate and adipate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, 1, 2-cyclohexanedicarboxylic acid diisononyl ester, triethylene glycol dicaprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1, 3-propanediol di-2-ethylbutyrate, 1, 4-butanediol di-2-ethylbutyrate, 1, 2-butanediol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, and mixtures thereof, Diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylvalerate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol di-caprylate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, dihexyl adipate, dioctyl adipate, hexyl adipate, diisononyl adipate, heptyl adipate, dibutyl sebacate, oil-modified alkyds, and adipates. Preferably, the plasticizer may be selected from triethylene glycol dicaprylate (3 GO).

In one embodiment, the polyvinyl butyral, the crosslinker system, and the plasticizer can be present in the PVB composition in amounts of 60 to 90 parts, 15 to 30 parts, and 2 to 10 parts by weight, respectively.

In one embodiment, the PVB composition further comprises 0.1-1 part of an ultraviolet absorber. When the PVB film is applied to laminated glass, the ultraviolet absorbent is added into the PVB film, so that the penetration effect of ultraviolet rays can be reduced, and the PVB film can be applied to building glass. In one embodiment, the ultraviolet absorber may be selected from one or more of a benzotriazole compound, a benzophenone compound, a triazine compound, a benzoate compound, and a hindered amine compound. In one embodiment, the benzotriazole compound may be selected from a UV326 agent or a UV-327 agent.

In one embodiment, the PVB composition further comprises 0.1 to 1 part of an antioxidant. The oxidation loss of the PVB film can be reduced by adding the antioxidant, and the service life of the PVB film is prolonged. In one embodiment, the antioxidant may be selected from 2, 2-bis [ [ [ [3- (2, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] oxy ] methyl ] propane-1, 3-dioxane ], 2, 6-di-tert-butyl-4-methylphenol (BHT), 1, 3-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 4,4' -thiobis (6-tert-butyl-3-methylphenol), 4' -dimethyl-6, 6' -di (tert-butyl) 2,2' -methylenebis (phenol), 2, 6-di-tert-butyl-cresol and 4,4' -butylidenebis- (6-tert-butyl) -3-methylphenol.

The embodiment of the invention also provides a preparation method of the PVB film, which comprises the following steps: and heating the PVB composition at 140-150 ℃ for extrusion molding.

Extrusion is a common process for producing PVB films, and the uniform mixing of polyvinyl butyral with other film components is a key issue limiting extrusion to produce high performance and quality PVB films. According to the cross-linking agent system in the PVB composition, disclosed by the embodiment of the invention, the acid anhydride is more easily dispersed to the polyvinyl butyral, so that the PVB composition is uniformly dispersed, the polyvinyl butyral is reinforced to be cross-linked, and the stability, cross-linking controllability and uniformity of a PVB film preparation process are improved.

The embodiment of the present invention further provides a laminated glass, where an interlayer film of the laminated glass includes the PVB film of the above embodiment or the PVB film prepared by the preparation method of the PVB film of the above embodiment.