JP7258280B2 - GLASS RESIN LAMINATED PRODUCT AND METHOD FOR MANUFACTURING SAME - Google Patents

Description

TECHNICAL FIELD The present invention relates to a glass resin laminate and a method for producing the same.

BACKGROUND ART Laminated glass capable of melting snow or frost adhering to a glass plate is known. For example, Patent Literature 1 discloses laminated glass, which is a glass resin laminate in which an intermediate film having a resin layer on one or both surfaces of a conductive layer is laminated between a pair of glass plates. By applying a voltage, a current flows through the conductive layer of the laminated glass, the conductive layer generates heat, and the heat melts the snow or frost adhering to the glass plate of the glass resin laminate.

JP 2018-145069 A

It is desired to raise the temperature of the glass resin laminate to 200° C. to 250° C. in order to melt snow and the like adhering to the glass plate in a short period of time. However, in Patent Document 1, since the resin layer is made of a thermoplastic resin, the durability of the resin layer at high temperatures is low, and there is a concern that the glass resin laminate cannot be used at high temperatures.

An object of the present invention is to provide a glass resin laminate having durability at high temperatures and a method for producing the same.

The glass resin laminate of the present invention comprises at least two glass plates, a silicone resin layer disposed between the two glass plates, and a silicone resin layer bonding the main surfaces of the two glass plates to each other, and the silicone resin layer. and a metal layer.

In the method for producing a glass resin laminate of the present invention, two glass plates are prepared, a metal layer is arranged on the main surface of one of the two glass plates, a silicone resin is applied to the metal layer, The other glass plate is bonded to the other glass plate with the silicone resin and the metal layer sandwiched therebetween, and the silicone resin is cured to form a silicone resin layer.

ADVANTAGE OF THE INVENTION According to this invention, the glass resin laminated body which has durability in high temperature, and its manufacturing method can be provided.

FIG. 1 is a perspective view of a glass resin laminate. FIG. 2 is a cross-sectional view along line II-II of FIG. FIG. 3 is a plan view showing an example of a metal layer. FIG. 4 is a schematic diagram showing steps of an embodiment of a method for manufacturing a glass resin laminate. FIG. 5 is a schematic diagram showing steps of an embodiment of a method for manufacturing a glass resin laminate. FIG. 6 is a schematic diagram showing steps of an embodiment of a method for manufacturing a glass resin laminate. FIG. 7 is a schematic diagram showing steps of an embodiment of a method for manufacturing a glass resin laminate.

An embodiment of the present invention will be described below with reference to the accompanying drawings. The invention is illustrated by the following embodiments. However, modifications can be made in many ways and other embodiments can be utilized without departing from the scope of the invention. Therefore, all changes that come within the scope of this invention are included in the claims. Here, parts indicated by the same symbols in the drawings are basically similar elements having similar functions.

In addition, in this specification, when a numerical range is expressed using "-", the upper and lower limits indicated by "-" are also included in the numerical range.

<Glass resin laminate>
As shown in FIGS. 1 and 2, the glass resin laminate 10 is disposed between two glass plates 12 and 14 and between the two glass plates 12 and 14, and a silicone resin layer 16 that joins the main surfaces of 14 together. A metal layer 18 is disposed on the silicone resin layer 16 .

(glass plate)
The glass plates 12 and 14 have two main surfaces facing each other and end surfaces connecting the two main surfaces. The glass plates 12 and 14 are arranged so that their main surfaces face each other.

Each of the glass plates 12 and 14 preferably has a thickness of 0.1 mm to 10 mm, more preferably 1 mm to 10 mm, even more preferably 1 mm to 5 mm. If the plate thickness of the glass plates 12 and 14 is 0.1 mm or more, the glass plates 12 and 14 are difficult to crack and easy to handle. Further, if the plate thickness of the glass plates 12 and 14 is 10 mm or less, heat is easily conducted to the surface of the substrate when generating heat from the viewpoint of heat conduction.

The total thickness of the glass plates 12 and 14 is preferably 0.5 mm to 20 mm, more preferably 2 mm to 15 mm, even more preferably 3 mm to 10 mm. . If the total plate thickness of the glass plates 12 and 14 is 0.5 mm or more, it is difficult to crack and easy to handle. Further, if the total thickness of the glass plates 12 and 14 is 20 mm or less, heat is easily conducted to the surface of the substrate when generating heat from the viewpoint of heat conduction.

The plate thickness of each of the glass plates 12 and 14 and the total plate thickness of the glass plates 12 and 14 are not limited to the ranges described above.

It is preferable that the thermal contraction rate of the glass plates 12 and 14 is small. The linear expansion coefficient at 50° C. to 350° C., which is an index of thermal shrinkage, is preferably 100×10 ⁻⁷ /° C. or less, more preferably 80×10 ⁻⁷ /° C. or less, and 50×10 ^-7 /°C or less is more preferable. The glass plates 12 and 14 having coefficients of linear expansion within the range described above can suppress the occurrence of warpage or breakage even when the glass resin laminate 10 is heated. The coefficient of linear expansion is measured according to JIS R3102 (1995) and can be measured with a differential thermal expansion meter. The lower limit of the coefficient of linear expansion at 50° C. to 350° C. is not particularly limited, but may be 30×10 ⁻⁷ /° C. or more.

The glass plates 12 and 14 may be manufactured by the float method or may be manufactured by the fusion method. The composition constituting the glass plates 12 and 14 is not particularly limited. The glass plates 12 and 14 are preferably made of soda lime glass, alkali-free borosilicate glass, borosilicate glass, high silica glass, and other oxide glasses containing silicon oxide as a main component.

The glass applied to the glass plates 12 and 14 is, for example, 40 to 80% SiO ₂ , 0 to 20% Al ₂ O ₃ , 0 to 22% Na ₂ O, K It preferably contains 0 to 10% of ₂ O, 0 to 14% of MgO, and 0 to 15% of CaO. Each component will be described below, and % means mol %.

SiO ₂ is known as a component that forms a network structure in the glass microstructure, and is a major component that constitutes glass. The content of SiO ₂ is preferably 40% or more, more preferably 56% or more, still more preferably 66% or more, and particularly preferably 68% or more. Also, the content of SiO ₂ is preferably 80% or less, more preferably 75% or less, and still more preferably 72% or less. When the content of SiO ₂ is 40% or more, the glass is superior in terms of stability and weather resistance. On the other hand, a SiO ₂ content of 80% or less is superior in terms of solubility and moldability.

Although Al ₂ O ₃ is not essential, it may be contained in order to improve the weather resistance of the glass. In addition, it has the effect of suppressing the infiltration of tin from the bottom surface during float molding. When Al ₂ O ₃ is contained, it is preferably 0.1% or more, more preferably 0.6% or more, and still more preferably 0.8% or more. Also, the content of Al ₂ O ₃ is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less, particularly preferably 3% or less, and most preferably 2% or less. When the content of _{Al 2 O 3} is 0.1% or more, the weather _resistance of the glass is improved. Since the temperature does not rise greatly, it is superior in terms of melting and molding on the production line.

The total SiO ₂ +Al ₂ O ₃ content of SiO ₂ and Al ₂ O ₃ is preferably 80% or less. If it exceeds 80%, the viscosity of the glass increases at high temperatures, and melting may become difficult. Also, SiO ₂ +Al ₂ O ₃ is preferably 68% or more. If it is less than 68%, the crack resistance when indented is lowered, and it is more preferably 70% or more.

Although Na ₂ O is not essential, it is a component that lowers the high-temperature viscosity and devitrification temperature of the glass and improves the meltability and formability of the glass. When Na ₂ O is contained, it is preferably 0.5% or more, more preferably 10% or more, and still more preferably 12% or more. Also, the content of Na ₂ O is preferably 22% or less, more preferably 16% or less, and still more preferably 14% or less. When the content of Na ₂ O is 0.5% or more, sufficient solubility and moldability can be obtained. On the other hand, when the content of Na ₂ O is 22% or less, sufficient weather resistance can be obtained.

K ₂ O is not essential, but it is a component that lowers the high-temperature viscosity and devitrification temperature of the glass and improves the meltability and formability of the glass. When K ₂ O is contained, it may be 0.1% or more, or 0.5% or more. Also, the content of K ₂ O is preferably 10% or less, more preferably 2% or less, and still more preferably 1% or less. When the K ₂ O content is 10% or less, good weather resistance is obtained.

MgO is not essential, but is a component that stabilizes the glass. The content of MgO is preferably 2% or more, more preferably 4% or more, and still more preferably 6% or more. Also, the MgO content is preferably 14% or less, more preferably 10% or less, and even more preferably 8% or less. When the MgO content is 2% or more, the chemical resistance of the glass is improved. Solubility at high temperatures is improved, and devitrification is less likely to occur. On the other hand, when the content of MgO is 14% or less, devitrification hardly occurs and a sufficient ion exchange rate can be obtained.

Although CaO is not essential, it may be contained in order to lower the high-temperature viscosity of the glass and improve its solubility. When CaO is contained, the amount is preferably 2% or more, more preferably 5% or more, and still more preferably 7% or more. Also, the CaO content is preferably 15% or less, more preferably 12% or less, and still more preferably 9% or less. If the CaO content is 15% or less, devitrification is less likely to occur.

SrO is not essential, but may be contained for the purpose of lowering the high-temperature viscosity of the glass and lowering the devitrification temperature. The amount of SrO when it is contained is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less.

BaO is not essential, but may be contained for the purpose of lowering the high-temperature viscosity of the glass and lowering the devitrification temperature. Since BaO has the effect of increasing the specific gravity of the glass, it is preferable not to contain it when intending to reduce the weight. When BaO is contained, the amount of BaO is preferably 3% or less, more preferably 2% or less, and still more preferably 1% or less.

The glass may contain other components. The total content of other components is preferably 5% or less, more preferably 3% or less, and typically 1% or less. The above-mentioned other components will be exemplified below.

ZnO may be contained, for example, up to 2% in order to improve the meltability of the glass at high temperatures. However, when it is produced by the float method, it is preferably not contained because it is reduced in the float bath and becomes a product defect.

B ₂ O ₃ may be contained in a range of less than 1% in order to improve meltability at high temperatures or glass strength. In general, _if an alkali component such _as Na ₂ O or K ₂ O and B ₂ O ₃ are contained at the same time, volatilization will be intense and bricks will be significantly eroded. In the present specification, "substantially free" means not containing anything other than unavoidable impurities mixed in from raw materials or the like, that is, intentionally not containing.

Li ₂ O is a component that lowers the strain point to facilitate stress relaxation and, as a result, makes it impossible to obtain stable compressive stress. %, more preferably 0.05% or less, particularly preferably less than 0.01%.

(Silicone resin layer)
The silicone resin layer 16 contains silicone resin. The silicone resin layer 16 is formed by curing silicone resin.

The silicone resin layer 16 preferably has a thickness of 0.01 mm to 1 mm, more preferably a thickness of 0.05 mm to 0.5 mm, and a thickness of 0.1 mm to 0.3 mm. is more preferred. When the thickness of the silicone resin layer 16 is 0.01 mm or more, the mesh can be uniformly impregnated with the silicone resin in the plane when the metal layer 18 has a mesh shape, which will be described later. Further, when the thickness of the silicone resin layer 16 is 1 mm or less, heat is easily transmitted when the glass resin laminate 10 is heated.

The linear expansion coefficient of the silicone resin layer 16 is preferably 1000×10 ⁻⁷ /° C. or less, more preferably 600×10 ⁻⁷ /° C. or less, and 400×10 ⁻⁷ /° C. or less. More preferred. If the linear expansion coefficient of the silicone resin layer 16 is 1000×10 ⁻⁷ /° C. or less, the glass plates 12 and 14 and the silicone resin layer 16 are less likely to separate when the glass resin laminate 10 is heated. The lower limit of the coefficient of linear expansion of the silicone resin layer 16 is not particularly limited, but may be 1×10 ⁻⁷ /° C. or more. The coefficient of linear expansion of the silicone resin layer 16 is measured according to JIS K 7197 (2012) and can be measured by TMA.

Silicone resins are classified into addition polymerization type, condensation type, and the like depending on the curing mechanism. The silicone resin can be applied to the silicone resin layer 16 by any curing mechanism. Among these, addition polymerization type silicone resins are preferred. Since the addition polymerization type silicone resin does not generate gas during curing, it is possible to suppress the generation of air bubbles in the silicone resin layer 16 .

The silicone resin of the embodiment preferably has, for example, the properties and composition shown below.

The molecular weight of the organoalkenylpolysiloxane used in the silicone resin is preferably from 1,000 to 5,000,000, more preferably from 2,000 to 3,000,000, and even more preferably from 3,000 to 1,000,000. Molecular weight means weight average molecular weight and can be measured by GPC (gel permeation chromatography).

The silicone resin preferably has, for example, the composition shown below.

The addition polymerization type silicone resin is a curable composition containing a linear organoalkenylpolysiloxane, a linear organohydrogenpolysiloxane, and additives such as a catalyst, and is cured by heating to become a cured silicone resin. . Specifically, the silicone resin layer 16 in the present embodiment comprises linear organopolysiloxane (a), which is a linear organoalkenylpolysiloxane, and linear organopolysiloxane (b), which is a specific organohydrogenpolysiloxane. It is a layer of a cured silicone resin obtained by curing an addition polymerization type silicone resin containing and. In general, compared with other silicone resins, addition polymerization type silicone resins are preferable because they undergo a curing reaction more easily and exhibit less curing shrinkage. Among them, the cured product of the addition polymerization type silicone resin in the present embodiment shows little change over time and is excellent in heat resistance. Generally, addition polymerization type silicone resins are used in the form of solvent type, emulsion type and non-solvent type compositions. Silicone resins in this embodiment can also be used in any type of composition.

Known addition polymerization type silicone resins containing linear organopolysiloxane (a) and linear organopolysiloxane (b) can be used. For example, Japanese Patent Publication No. 2005-509711 (International Publication No.: WO2003/044084) and its cited documents disclose an addition polymerization type silicone resin for forming a water-repellent and peelable silicone film on paper or a plastic film. is described. The silicone resin used for forming the silicone resin layer 16 will be described in detail below.

<Linear Organopolysiloxane (b)>
The silicone resin in this embodiment preferably contains linear organopolysiloxane (a) and linear organopolysiloxane (b). Among these, the linear organopolysiloxane (b) is one type of organohydrogenpolysiloxane. The linear organopolysiloxane (b) is a linear organopolysiloxane having at least three silicon-bonded hydrogen atoms per molecule, and at least one of the silicon-bonded hydrogen atoms is at a molecular terminal. is a linear organopolysiloxane present at the silicon atoms of

In general, the monofunctional units at both ends of a linear organopolysiloxane are called M units, and the difunctional units other than both ends are called D units. The structure of polysiloxane is represented by M(D) _nM . Moreover, when representing the average composition of each unit, it may be represented by M ₂ (D) _n .

In the linear organopolysiloxane (b) in this embodiment, at least one of the two M units preferably has a silicon-bonded hydrogen atom. A more preferred linear organopolysiloxane (b) has a hydrogen atom bonded to a silicon atom in each of the two M units, and some of the n D units are also bonded to a silicon atom. It is a linear organopolysiloxane in which hydrogen atoms are present. Linear organopolysiloxane (b) can also be used in combination with other linear organohydrogenpolysiloxanes. Other linear organohydrogenpolysiloxanes include linear organohydrogenpolysiloxanes in which no silicon-bonded hydrogen atoms are present in the M units and silicon-bonded hydrogen atoms are present in only a portion of the D units. It is siloxane.

As the linear organopolysiloxane (b) or the mixture of the linear organopolysiloxane (b) and another linear organohydrogenpolysiloxane, a linear organopolysiloxane having an average composition represented by the following formula (1) is used. preferable. The organohydrogenpolysiloxane represented by this average composition formula is hereinafter referred to as organohydrogenpolysiloxane (1).

(M ¹ ) _α (M ² ) _β (D ¹ ) _γ (D ² ) _δ Formula (1)
provided that M ¹ is an M unit in which no silicon-bonded hydrogen atom exists, M ² is an M unit in which a silicon-bonded hydrogen atom exists, D ¹ is a D unit in which a silicon-bonded hydrogen atom does not exist, and D ² represents a D unit in which a hydrogen atom bonded to a silicon atom is present, α is a number of 0 or more and less than 2, β is a number other than 0 but 2 or less and α + β = 2, γ is a number greater than 0, δ is A number greater than or equal to 0 and γ+δ=n. In the more preferred organohydrogenpolysiloxane (1), α is a number of 0 or more and less than 1, β is a number of 1 or more and 2 or less, γ is a number of 1 or more, and δ is a number of 1 or more. The organohydrogenpolysiloxane represented by Formula (5) described in WO 2007/018028 pamphlet is a compound with β=0.

The linear organopolysiloxane (b) is preferably a compound in which β is a number of 1 or more and 2 or less in the above formula (1). A more preferable linear organopolysiloxane (b) is a compound in which α is a number of 0 or more and less than 1, β is a number of 1 or more and 2 or less, γ is a number of 1 or more, and δ is a number of 1 or more.

The ^M2 unit may have two or three hydrogen atoms bonded to a silicon atom, but preferably has one. A ^D2 unit may have two hydrogen atoms bonded to a silicon atom, but preferably has one. The ^M1 unit, ^D1 unit, preferred ^M2 unit, and preferred ^D2 unit are preferably represented by the following formulas. R ¹ to R ⁵ each independently represent an alkyl group having 4 or less carbon atoms, a fluoroalkyl group, or a phenyl group. R ¹ to R ⁵ are preferably all methyl groups.

When ^D2 units are present (when δ is not 0), γ/δ, which is the abundance ratio of ^D1 and ^D2 , is an index representing the density of hydrogen atoms bonded to silicon atoms in the molecule. The abundance ratio (γ/δ) is preferably 0.2-30, more preferably 0.5-20. If this abundance ratio is too small, the residual amount of hydrogen atoms bonded to unreacted silicon atoms in the cured silicone resin increases, resulting in greater change over time of the cured silicone resin and the risk of lowering heat resistance. There is On the other hand, if the abundance ratio is too large, the crosslink density of the cured silicone resin decreases, which may lead to a decrease in heat resistance.

β/δ representing the abundance ratio of ^M2 units and ^D2 units is preferably 15≦(β/δ)×1000≦1500. More preferably, 15≦(β/δ)×1000≦1000, and even more preferably 15≦(β/δ)×1000≦500. When (β/δ)×1000 is less than 15, the molecular weight becomes large, or the steric hindrance of the functional group becomes large, and the reactivity may be lowered, which may lower the heat resistance. On the other hand, if (β/δ)×1000 is more than 1500, the crosslink density becomes small, and there is a possibility that a cured silicone resin having sufficient physical properties such as strength cannot be obtained.

The above formula (1) shows the average composition of the organosiloxane units in the organohydrogenpolysiloxane, and the individual molecules of the linear organopolysiloxane (b) are represented by α being an integer of 0 or 1 and β being An integer of 1 or 2, α+β=2, γ is an integer of 1 or more, and δ is an integer of 0 or more.

Each molecule of the organohydrogenpolysiloxane other than the linear organopolysiloxane (b) is an organohydrogenpolysiloxane in which α is 2, β is 0, γ is an integer of 0 or more, and δ is an integer of 1 or more. be. In addition, when both ^D1 and ^D2 exist in a large number in these molecules, the arrangement of ^D1 and ^D2 may be a random copolymer chain structure or a block copolymer chain structure. Since a copolymer chain is normally formed by ring-opening polymerization of cyclic siloxane, it is considered that the ring-opened cyclic siloxane blocks are randomly copolymerized.

As described above, the linear organopolysiloxane (b) includes not only organohydrogenpolysiloxanes in which each molecule is a linear organopolysiloxane (b), but also linear organopolysiloxanes (b) and other organohydrogens. A mixture of polysiloxanes (having an average composition represented by the above formula (1)) may also be used. In that case, the linear organopolysiloxane (b) preferably accounts for 20 mol % or more of the total number of moles of the organohydrogenpolysiloxane used. If it is less than 20 mol %, hydrogen atoms bonded to silicon atoms tend to remain, which is not preferred. The content of the linear organopolysiloxane (b) is preferably 50 mol % or more, more preferably 80 mol % or more, in terms of the heat resistance of the cured silicone resin and the stability of the silicone resin layer 16 over time.

<Linear organopolysiloxane (a)>
The silicone resin in the present embodiment preferably contains linear organopolysiloxane (a) that reacts with linear organopolysiloxane (b). Linear organopolysiloxane (a) is a linear organopolysiloxane having at least two alkenyl groups per molecule. A linear organopolysiloxane having an alkenyl group is hereinafter also referred to as an organoalkenylpolysiloxane.

Although the alkenyl group is not particularly limited, examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a butenyl group, a pentenyl group, a hexynyl group, and the like. groups are preferred.

In the linear organopolysiloxane (a), the alkenyl groups may be present on the M units or the D units, and may be present on both the M and D units. From the viewpoint of curing speed, it is preferably present in at least M units, and preferably present in both two M units. In addition, the higher the molecular weight of the organoalkenylpolysiloxane, which has an alkenyl group only in the M unit, the lower the alkenyl group concentration per molecule and the crosslink density of the cured silicone resin. Therefore, it is preferable that some of the D units as well as the M units have an alkenyl group.

As the linear organopolysiloxane (a), a linear organopolysiloxane having an average composition represented by the following formula (2) is preferred.

(M ¹ ) _a (M ³ ) _b (D ¹ ) _c (D ³ ) _d Equation (2)
However, M ¹ is an M unit having no alkenyl group (the same as the above M ¹ unit), M ³ is an M unit having an alkenyl group bonded to a silicon atom, D ¹ is a D unit having no alkenyl group (the above D ¹ unit), and D ³ represents a D unit having an alkenyl group bonded to a silicon atom, a is a number of 0 to 2, b is a number of 0 to 2 and a + b = 2, c is a number of 0 or more, d is a number of 0 or more and c+d=n (where b+d is 2 or more). In the more preferred organoalkenylpolysiloxane represented by formula (2), a is a number of 0 or more and less than 1, b is a number of 1 or more and 2 or less, c is a number of 1 or more, and d is a number of 1 or more.

The ^M3 unit may have 2 or 3 alkenyl groups bonded to a silicon atom, but preferably has 1. The ^D3 unit may have two silicon-bonded alkenyl groups, but preferably has one. A vinyl group is preferred as the alkenyl group. The ^M1 unit, ^D1 unit, preferred ^M3 unit, and preferred ^D3 unit are preferably represented by the following formulas. Each of R ¹ to R ⁵ independently represents an alkyl group having 4 or less carbon atoms, a fluoroalkyl group, or a phenyl group as described above. R ¹ to R ⁵ are preferably all methyl groups.

Formula (2) above shows the average composition of the organosiloxane units in the organoalkenylpolysiloxane, and the individual molecules of linear organopolysiloxane (a) are represented by the following: a is an integer of 0 or 1; b is 1; Or an integer equal to 2, a+b=2, c is an integer of 1 or more, and d is an integer of 0 or more. Since the linear organopolysiloxane (a) has two or more alkenyl groups per molecule, b+d is 2 or more. Organoalkenylpolysiloxane (a) may be a mixture with other organoalkenylpolysiloxanes, but usually only organoalkenylpolysiloxane (a) is used. However, the organoalkenylpolysiloxane (a) may be a mixture of two or more organoalkenylpolysiloxanes (a). A more advantageous effect can be obtained by using two kinds of organoalkenylpolysiloxanes having different La values together.

Further, as in the case of the organohydrogenpolysiloxane, the above formula (2) indicates that when there are many D ¹ and D ³ in the organoalkenylpolysiloxane, the arrangement of D ¹ and D ³ is a random copolymer chain It may be a structure or a block copolymer chain structure. As the organoalkenylpolysiloxane (a), an organoalkenylpolysiloxane represented by the formula (3) or (4) described in International Publication No. 2007/018028 can be used.

The weight average molecular weight Mw of the organoalkenylpolysiloxane (a) is preferably in the range of 1,000≤Mw≤5,000,000. Mw is more preferably 2,000≦Mw≦3,000,000, and more preferably 3,000≦Mw≦1,000,000. When Mw is within this range, volatilization does not occur during heat curing, and workability is improved without excessively high viscosity.

Furthermore, it is preferably in the range of 0.001≦La≦1.0 in terms of the number of equivalents La of alkenyl groups per 100 grams of the organoalkenylpolysiloxane (a). La is more preferably 0.0015≦La≦0.9, more preferably 0.002≦La≦0.9. By setting La within this range, the heat resistance of the cured silicone resin is improved, and the stability over time of the peel strength between the cured silicone resin layer and the glass substrate is improved.

The content ratio of the linear organopolysiloxane (a) and the linear organopolysiloxane (b) in the silicone resin is not particularly limited. It is preferable to adjust the molar ratio (hydrogen atoms/alkenyl groups) of all alkenyl groups in the organopolysiloxane (a) to 0.7 to 1.05. Among them, it is preferable to adjust the content ratio so as to be 0.8 to 1.0. If the molar ratio of silicon-bonded hydrogen atoms to alkenyl groups is less than 0.7, the crosslink density of the cured silicone resin decreases, which may cause problems such as heat resistance.

When the molar ratio of hydrogen atoms bonded to silicon atoms to alkenyl groups exceeds 1.05, moisture in the air gradually penetrates from the edges of the laminate when left for a long period of time, and unreacted components in the cured silicone resin There is concern that the hydrosilyl groups (Si—H groups) will be hydrolyzed, and some kind of reaction will proceed with the silanol groups on the surface of the glass substrate. Therefore, it is preferable that substantially no hydrogen atoms bonded to unreacted silicon atoms remain in the silicone resin layer 16 .

<Other components>
Various additives may be contained in the silicone resin in the present embodiment, if necessary, as long as the effects of the present invention are not impaired. As an additive, it is usually preferable to use a catalyst (addition polymerization catalyst) that promotes the reaction between a silicon-bonded hydrogen atom and an alkenyl group. As this catalyst, it is preferable to use a platinum group metal-based catalyst. Examples of the platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and it is particularly preferable to use a platinum-based catalyst from the viewpoint of economy and reactivity. A well-known thing can be used as a platinum-type catalyst. Specifically, platinum fine powder, platinum black, chloroplatinic acid such as chloroplatinic acid and chloroplatinic acid, platinum tetrachloride, alcohol compounds of chloroplatinic acid, aldehyde compounds, or platinum olefin complexes, alkenyl Examples include siloxane complexes and carbonyl complexes.

The weight ratio of the catalyst to the total weight of linear organopolysiloxane (a) and linear organopolysiloxane (b) is preferably 2 to 400 ppm. More preferably 5 to 300 ppm, still more preferably 8 to 200 ppm.

The silicone resin in the present embodiment is preferably used in combination with an activity inhibitor (a compound also called a reaction inhibitor, a retarder, etc.) that has the effect of suppressing the catalytic activity for the purpose of adjusting the catalytic activity together with the catalyst. Examples of activity inhibitors include various organic nitrogen compounds, organic phosphorus compounds, acetylenic compounds, oxime compounds, and organic chloro compounds. Furthermore, if necessary, inorganic fillers such as various types of silica, calcium carbonate, iron oxide, etc. may be contained within a range that does not impair the effects of the present invention.

(metal layer)
The material and shape of the metal layer 18 are not limited as long as the metal layer 18 can pass an electric current and generate heat by the electric current.

As a material for the metal layer 18, a metal such as iron, copper, brass, stainless steel (SUS steel), aluminum, nickel, tungsten, or nichrome, or a metal represented by an alloy is applied.

The metal layer 18 preferably has a thickness of 0.001 mm to 0.5 mm, more preferably has a thickness of 0.01 mm to 0.2 mm, and has a thickness of 0.01 mm to 0.1 mm. is more preferred. If the thickness of the metal layer 18 is 0.001 mm or more, the wiring necessary for generating heat in the glass resin laminate 10 is less likely to break. Further, if the thickness of the metal layer 18 is 0.500 mm or less, the metal layer 18 can be impregnated with a silicone resin when the metal layer 18 has a mesh shape, which will be described later.

Regarding shape, the metal layer 18 preferably has a mesh shape, for example, as shown in the plan view of FIG. The mesh-shaped metal layer 18 can improve the visible light transmittance of the glass resin laminate 10 . The transparency of the glass resin laminate 10 is increased, and the opposite side of the glass resin laminate 10 can be easily visually recognized.

The mesh shape is a mesh shape in which openings 22 are formed by a plurality of metal wires 20 . The opening 22 is formed by weaving a plurality of wire rods 20, for example. The method of weaving the plurality of wire rods 20 is not particularly limited. If the metal layer 18 is mesh-shaped, the formed openings 22 preferably penetrate the metal layer 18 .

The mesh-shaped metal layer 18 preferably has a wire diameter D (wire diameter of the wire 20) of 0.001 mm to 0.1 mm and a void ratio of 5% to 60%, and is 0.010 mm to 0.05 mm. It is more preferable to have a wire diameter D (wire diameter of the wire rod 20) of 10% to 50%, and a wire diameter D (wire diameter of the wire rod 20) of 0.01 mm to 0.025 mm, and 20% It is even more preferred to have a void fraction of ~40%. The mesh-shaped metal layer 18 within the range described above can improve the visible light transmittance of the glass resin laminate 10 . Here, the void ratio is the ratio of the area of the openings 22 of the metal layer 18 to the total area of the plurality of metal wires 20 and the openings 22 of the metal layer 18 .

The shape of the opening 22 of the metal layer 18 is shown as a square, but the shape is not particularly limited. can.

As shown in FIGS. 1 and 2, the glass resin laminate 10 of the present embodiment has a portion 18A where the metal layer 18 protrudes from the edge of the silicone resin layer 16 (hereinafter referred to as protruding portion 18A). The projecting portion 18A is a region of the metal layer 18 that is not covered with the silicone resin layer 16. As shown in FIG. The projecting portion 18A is electrically connected to a terminal (not shown). A voltage is applied from the terminal to the metal layer 18 through the projecting portion 18A, current flows through the metal layer 18, and heat is generated. The heat generated in the metal layer 18 melts snow or the like adhering to the surfaces of the glass plates 12 and 14 of the glass resin laminate 10 .

Since the glass resin laminate 10 includes the silicone resin layer 16, the temperature of the glass resin laminate 10 can be raised to 200° C. to 250° C., and snow and the like can be melted in a short period of time.

Next, preferred aspects of the glass resin laminate 10 will be described. The ratio (Tr/Tm) of the thickness Tr of the silicone resin layer 16 to the thickness Tm of the metal layer 18 is preferably in the range of 1 to 5, more preferably in the range of 1 to 3, and more preferably in the range of 1 to 2. is more preferably in the range of Warping of the glass resin laminate 10 can be suppressed by setting the ratio (Tr/Tm) within the above range.

The difference in coefficient of linear expansion between the glass plates 12 and 14 of the glass resin laminate 10 and the silicone resin layer 16 increases. When the glass resin laminate 10 generates heat, there is a concern that warpage may occur due to the difference in coefficient of linear expansion between the glass plates 12 and 14 and the silicone resin layer 16 .

On the other hand, a metal layer 18 is arranged on the silicone resin layer 16 of the glass resin laminate 10 . Since the metal layer 18 has a coefficient of linear expansion smaller than that of the silicone resin layer 16, the metal layer 18 acts to reduce the dimensional change of the silicone resin layer 16 due to heat. By adjusting the ratio of the thickness Tm of the metal layer 18 to the thickness Tr of the silicone resin layer 16, the apparent linear expansion coefficient of the silicone resin layer 16 can be reduced. As a result, the difference in coefficient of linear expansion between the glass plates 12 and 14 and the silicone resin layer 16 is reduced, and warping of the glass resin laminate 10 can be suppressed.

The difference between the coefficient of linear expansion of the glass plates 12 and 14 and the coefficient of linear expansion of the silicone resin layer 16 is preferably 1000×10 ⁻⁷ /° C. or less, more preferably 600×10 ⁻⁷ /° C. or less. It is preferably 400×10 ⁻⁷ /° C. or less, more preferably 400×10 −7 /° C. or less. A difference from the coefficient of linear expansion means an absolute value. If the difference in coefficient of linear expansion is within the above range, warping of the glass resin laminate 10 can be suppressed. By suppressing the warp of the glass resin laminate 10, the glass plates 12, 14 and the silicone resin layer 16 are less likely to separate, and furthermore, when the glass plates 12, 14 are supported by a frame, the glass plates 12, 14 are separated from the frame. Hard to come off.

The surface compressive stress of the silicone resin layer 16 of the glass resin laminate 10 is preferably 500 MPa or less, more preferably 300 MPa or less, and even more preferably 100 MPa or less. If the surface compressive stress of the silicone resin layer 16 is 500 MPa or less, the difference between the surface compressive stress of the glass plates 12 and 14 is small, and the glass resin laminate 10 is less likely to warp. The lower the surface compressive stress of the silicone resin layer 16 is, the better. Although the lower limit is not particularly limited, it may be 0 MPa or more, 1 MPa or more, or 10 MPa or more. The surface compressive stress of the silicone resin layer 16 is measured by a thin film stress measuring device (for example, FLX-2320-S manufactured by Toho Technology Co., Ltd.).

It is preferable that the two glass plates 12 and 14 of the glass resin laminate 10 have the same plate thickness. By making the two glass plates 12 and 14 the same thickness, there is almost no difference in linear expansion coefficient between the glass plates 12 and 14 with the silicone resin layer 16 interposed therebetween. Therefore, warping of the glass resin laminate 10 due to the difference in coefficient of linear expansion is suppressed. The same plate thickness includes completely the same plate thickness and the same plate thickness with a tolerance specified in JIS (Japanese Industrial Standards) R3202:2011.

The plate thicknesses of the two glass plates 12 and 14 of the glass resin laminate 10 may be different. When the glass resin laminate 10 is used as a window, if a thick glass plate 12 (or 14) is used on the outside, impact resistance when an object hits the glass plate can be improved. When a thick glass plate 12 (or 14) is used inside, the heat resistance can be improved. Different plate thickness means other than "same plate thickness" as described above.

<Method for producing glass resin laminate>
Next, a method for manufacturing the glass resin laminate 10 will be described with reference to FIGS. 4 to 7. FIG. Two glass plates 12 and 14 are prepared, and a metal layer 18 is placed on the main surface of one glass plate 14 of the two glass plates 12 and 14 as shown in FIG. The metal layer 18 may be arranged in contact with the main surface of the glass plate 14 or may be arranged at a certain distance from the main surface of the glass plate 14 . In FIG. 4, an arrangement in which the metal layers 18 are spaced apart is shown.

Next, a pre-prepared silicone resin 16A is applied to the metal layer 18, as shown in FIG. The silicone resin 16A is applied over the entire main surface of the glass plate 14 . On the other hand, the silicone resin 16A is not applied to the areas where the projecting portions 18A of the metal layer 18 are to be formed. It is preferable to remove air bubbles present in the silicone resin 16A.

Next, as shown in FIG. 6, the other glass plate 12 is bonded to the one glass plate 14 with the silicone resin 16A and the metal layer 18 interposed therebetween. In the lamination, one sides of the glass plate 12 and the glass plate 14 are aligned with each other, and the glass plate 12 and the glass plate 14 are not parallel and obliquely arranged. The bonding is performed, for example, by gradually bringing the glass plate 12 closer to the glass plate 14 with one side as a fulcrum. By doing so, it becomes easier for the air bubbles to escape from the silicone resin 16A. When the glass plates 12 and 14 are aligned side to side, aligning the short sides makes it easier to remove air bubbles.

Next, as shown in FIG. 7, the silicone resin 16A is cured to form the silicone resin layer 16. Next, as shown in FIG. The silicone resin 16A is cured by being placed in an environment of, for example, 40° C. to 80° C. for 1 hour to 15 hours and then at 100° C. to 200° C. for 1 hour to 12 hours to form the silicone resin layer 16. be. In addition, in the manufacturing method of a glass-resin laminated body, any process or all processes are performed in a pressure-reduced environment as needed.

By curing under the above environment, the silicone resin layer 16 can achieve a surface compressive stress of 0 MPa to 500 MPa.

The glass resin laminate of the embodiment can be applied to places where it is necessary to melt snow, such as automobiles, railroad vehicles, airplanes, buildings, vending machines, roofs, walls, and windows. Although the embodiments of the present invention have been described, the present invention is not limited to the above examples, and includes various improvements and modifications without departing from the gist of the present invention.

DESCRIPTION OF SYMBOLS 10... Glass resin laminate, 12, 14... Glass plate, 16... Silicone resin layer, 16A... Silicone resin, 18... Metal layer, 18A... Protruding portion, 20...・Wire, 22 ... opening

Claims (9)

A glass resin laminate,
at least two glass plates;
a silicone resin layer disposed between the two glass plates and bonding the main surfaces of the two glass plates;
a metal layer disposed on the silicone resin layer;
has
The silicone resin layer has a surface compressive stress of 0 MPa to 300 MPa,
The ratio of the thickness of the silicone resin layer to the thickness of the metal layer is 1 to 5,
The silicone resin of the silicone resin layer is an addition polymerization type,
The organoalkenylpolysiloxane used in the silicone resin layer has a weight average molecular weight of 1000 to 5000000,
The silicone resin layer contains a platinum group metal-based catalyst,
Glass resin laminate. 2. The glass resin laminate according to claim 1, wherein the difference between the coefficient of linear expansion of said silicone resin layer and the coefficient of linear expansion of said glass plate is 1000×10 ⁻⁷ /° C. or less. The glass resin laminate according to claim 1 or 2, wherein the glass plate is soda lime glass. The glass resin laminate according to any one of claims 1 to 3, wherein the two glass plates have the same plate thickness. The glass resin laminate according to any one of claims 1 to 3, wherein the two glass plates have different plate thicknesses. The glass resin laminate according to any one of claims 1 to 5, wherein the metal layer has a mesh shape. 7. The glass resin laminate according to claim 6, wherein the metal layer has a wire diameter of 0.001 mm to 0.1 mm and a void ratio of 5% or more and 60% or less. The glass resin laminate according to any one of claims 1 to 7, wherein the metal layer has a portion protruding from an end of the silicone resin layer. Prepare two glass plates,
Arranging a metal layer on the main surface of one of the two glass plates,
applying a silicone resin to the metal layer;
bonding the other glass plate to the one glass plate with the silicone resin and the metal layer sandwiched therebetween;
A method for producing a glass resin laminate, wherein the silicone resin is cured to form a silicone resin layer,
The silicone resin layer has a surface compressive stress of 0 MPa to 300 MPa,
The ratio of the thickness of the silicone resin layer to the thickness of the metal layer is 1 to 5,
The silicone resin of the silicone resin layer is an addition polymerization type,
The organoalkenylpolysiloxane used in the silicone resin layer has a weight average molecular weight of 1000 to 5000000,
The silicone resin layer contains a platinum group metal-based catalyst,
The silicone resin is cured by being placed in an environment at 40° C. to 80° C. for 1 hour to 15 hours, and then at 100° C. to 200° C. for 1 hour to 12 hours.
A method for producing a glass resin laminate.

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