Filler-containing composition

Abstract

The present invention belongs to the technical field of solar panels, and provides a filler-containing composition. The filler-containing composition comprises a PVB resin and an inorganic transparent filler; and the transparent filler is prepared after being surface treated with a silane coupling agent. Amino groups (including RNH2-primary amine, R2NH-secondary amine and R3N-tertiary amine), aldehyde groups, alkylene groups and carbamate groups suitable for surface treatment of inorganic transparent filler are screened out by means of experimental research. The fillers are added to the PVB resin to prepare a PVB adhesive film, such that a sharp decrease in the elongation at break and / or tensile strength of the PVB adhesive film can be significantly alleviated, which has a significant technical effect.

Description

Composition comprising filler TECHNICAL FIELD

[0001] The present application relates to a composition comprising filler, belonging to the technical field of solar backsheet. BACKGROUND

[0002] Safety glass, also known as laminated glass, is a kind of composite glass formed by bonding between two or more layers of glass through the setting of PVB film, which can absorb impact energy and reduce the flying of broken fragments, and is widely used in automobiles and buildings.

[0003] With the progress of society, people's requirements for laminated glass are also getting higher and higher. The main performance requirements for PVB film are improved. It requires: 1, good adhesion to glass; 2, good tensile strength and elongation at break; 3, good light transmittance; 4, good sound insulation performance; 5, low water vapor transmission rate.

[0004] In order to maintain the high light transmittance of PVB and reduce the water vapor transmission rate, improve the performance of PVB Young's modulus, etc., transparent fillers are often added in PVB resin. However, it is difficult for transparent fillers such as fumed silica, glass flake, transparent mica, and transparent ceramic to completely disperse uniformly in PVB resin and form chemical bonds or physical bonds with PVB, thereby causing the attenuation of other properties.

[0005] A Chinese invention patent application with application number CN 202310805999.6 discloses a composite PVB resin powder, which comprises: PVB resin 80-120 parts, plasticizer 10-20 parts, modified four-needle zinc oxide whisker 0.2-1 part, antioxidant 0.1-0.3 part, ultraviolet absorber 0.1-0.3 part, and surface tension regulator 0.1-0.2 part. The four-needle zinc oxide whisker in the patent is used as a sound insulation aid. The four-needle zinc oxide whisker also has the problem of not being able to disperse uniformly. Therefore, the four-needle zinc oxide whisker is grafted and modified in the invention, so that its surface changes from hydrophilic and oleophobic to lipophilic and hydrophobic, thereby improving the dispersibility of the four-needle zinc oxide whisker in PVB. However, grafting modification is relatively complex, and different fillers need to be modified by completely different methods, and it is difficult to learn from each other.

[0006] In fact, the field has more adopted silane coupling agents for surface treatment when solving the problem of dispersibility. However, there are various types of silane coupling agents, and different types of fillers require different silane coupling agents, and the base resin also has a great impact on the dispersion of the fillers in it. There is no research report in the field on the surface treatment of transparent fillers to improve their dispersibility in PVB resin and form chemical bonds or physical bonds with PVB.

[0007] SUMMARY

[0008] The present application solves the above technical problems, and provides a composition containing fillers. The composition containing fillers provided by the present application significantly improves the dispersibility of fumed silica and glass flake in PVB, so that the prepared PVB film has almost no loss in tensile strength and elongation at break compared with PVB film without fillers.

[0009] The technical solution of the present application to solve the above problems is as follows:

[0010] The composition containing fillers comprises PVB resin and transparent fillers; the transparent fillers are prepared after surface treatment with silane coupling agent.

[0011] As a preferred embodiment of the above technical solution, the composition further comprises PVB plasticizer.

[0012] As a preferred embodiment of the above technical solution, the PVB plasticizer is selected from at least one of dioctyl phthalate (DOP), triethylene glycol diisooctylate (3G8), 1,4-cyclohexane dicarboxylic acid dioctyl ester (CHC), fatty alcohol polyoxyethylene ether, and alkyl phenol polyoxyethylene ether.

[0013] As a preferred embodiment of the above technical solution, the mass ratio of PVB resin to PVB plasticizer is 100:(25-50).

[0014] As a preferred embodiment of the above technical solution, the transparent fillers are glass flake surface-treated with silane coupling agent.

[0015] As a preferred embodiment of the above technical solution, the addition amount of transparent fillers is not more than 40wt% of the total mass of the composition.

[0016] In the prior art, transparent fillers such as glass flake are often used in coatings to improve the protective performance of the coatings. In the above technical solution of the present application, glass flake is added to PVB resin to reduce the water vapor transmission rate of PVB film. However, it is found in experiments that the addition of glass flake causes the elongation at break of PVB film to decrease sharply from about 250% to below 60%. The inventors believe that this is mainly caused by the fact that glass flake cannot be uniformly dispersed in PVB resin and cannot form chemical bonds or physical bonds with PVB.

[0017] In order to solve the problem of dispersibility and make transparent fillers form chemical bonds or physical bonds with PVB, the present application proposes a pretreatment scheme using silane coupling agent, and selects the most suitable silane coupling agent from the prior art.

[0018] As the preferred technical solution of the above, the silane coupling agent is a silane coupling agent with active groups selected from one of amino (including RNH2- primary amine, R2NH- secondary amine, R3N- tertiary amine), aldehyde group, olefin group, and carbamate group.

[0019] When the matrix resin is PVB, and the silane coupling agent is selected from one of amino (including RNH2- primary amine, R2NH- secondary amine, R3N- tertiary amine), aldehyde group, olefin group, and carbamate group, the decrease of the elongation at break can be significantly slowed down.

[0020] As the preferred technical solution of the above, the surface treatment refers to dispersing the transparent filler and the silane coupling agent into an organic solvent, heating for 1-10 hours, and then solid-liquid separation and drying.

[0021] In summary, the present application has the following beneficial effects:

[0022] 1. The elongation at break is a symbol of the softness of PVB. Through experimental research, the present application screens out the silane coupling agent with aldehyde group, carbamate group, olefin group, and amino group suitable for the surface treatment of the transparent filler; and after the filler is added into the PVB resin and the PVB film is made, the elongation at break and / or the tensile strength of the PVB film can be significantly slowed down, which has a significant technical effect.

[0023] 2. Through experimental research, the present application finds that in the composition formed by the PVB added with the plasticizer, the addition of the surface-treated fumed silica can significantly improve the adhesion of the polymer composition to glass.

[0024] 3. Through experimental research, the present application finds that the PVB film made of the composition formed by the PVB added with the plasticizer and further added with the transparent filler has excellent light transmittance, and the light transmittance is greater than 90% and the haze is less than 0.8%. DETAILED DESCRIPTION

[0025] The present embodiment is only an explanation of the present application, and is not a limitation of the present application. Any change made by the person skilled in the art after reading the specification of the present application shall be protected by the patent law as long as it is within the scope of the claims.

[0026] Example 1

[0027] The composition containing fillers comprises 40 g of polyvinyl butyral resin PVB, 7.0 g of triethylene glycol diisooctanoate 3G8, 4.6 g of 1,4-cyclohexane dicarboxylic acid dioctyl ester CHC, and 22.1 g of glass flake. The PVB comprises 24.0 g of 18K18 and 16.0 g of 8K18, wherein 18K18 refers to a PVB with a molecular degree of polymerization of about 1800 and an -OH content of about 18 wt%, and 8K18 refers to a PVB with a molecular degree of polymerization of about 800 and an -OH content of about 18 wt%.

[0028] The glass flake is pre-surface treated with a silane coupling agent.

[0029] The specific method is as follows: the glass flake and the silane coupling agent are dispersed with toluene, heated to about 110°C, and kept for 6 h, and then solid-liquid separation is performed by using a centrifuge, and the solid phase is baked at 85°C for 12 h.

[0030] In this embodiment, the silane coupling agent is numbered S1, and specifically is triethoxysilane-based undecanal, with a CAS number of 116047-42-8.

[0031] The composition is heated to 90°C, vacuum stirring is performed until complete compatibility, and then cast extrusion is performed to obtain a PVB film with a thickness of 0.8 mm.

[0032] Example Two

[0033] The composition is heated to 90°C, vacuum stirring is performed until complete compatibility, and then cast extrusion is performed to obtain a PVB film with a thickness of 0.8 mm.

[0034] In this embodiment, the silane coupling agent is numbered S2, and specifically is triethoxysilane-based undecanal glycol acetal, with a CAS number of 866935-66-2.

[0035] Example Three

[0036] The composition is heated to 90°C, vacuum stirring is performed until complete compatibility, and then cast extrusion is performed to obtain a PVB film with a thickness of 0.8 mm.

[0037] In this embodiment, the silane coupling agent is numbered S3, and specifically is 3-(trimethoxysilyl)propylamine, with a CAS number of 13822-56-5.

[0038] Example Four

[0039] The composition is heated to 90°C, vacuum stirring is performed until complete compatibility, and then cast extrusion is performed to obtain a PVB film with a thickness of 0.8 mm.

[0040] In this embodiment, the silane coupling agent is numbered S4, and specifically is 1-[3-(trimethoxysilyl)propyl]urea, with a CAS number of 23843-64-3.

[0041] Example Five

[0042] The composition is heated to 90°C, vacuum stirring is performed until complete compatibility, and then cast extrusion is performed to obtain a PVB film with a thickness of 0.8 mm.

[0043] In this example, silane coupling agent number S5, specifically N-(2-aminoethyl)- 11-aminoundecyltrimethoxysilane, CAS number 121772-92-7.

[0044] Example Six

[0045] The same as Example One, except that:

[0046] In this example, silane coupling agent number S6, specifically 3-(N-allylamino)propyltrimethoxysilane, CAS number 31024-46-1.

[0047] Example Seven

[0048] The same as Example One, except that:

[0049] In this example, silane coupling agent number S7, specifically 3-[bis(2- hydroxyethyl)amino]propyltriethoxysilane, CAS number 7538-44-5.

[0050] Example Eight

[0051] The same as Example One, except that:

[0052] In this example, silane coupling agent number S8, specifically N3-[3- (dimethoxymethylsilyl)propyl]-N1,N1-dimethyl-1,3-propanediamine, CAS number 224638-27-1.

[0053] Example Nine

[0054] The same as Example One, except that:

[0055] In this example, silane coupling agent number S9, specifically 3-glycidyloxypropyltriethoxysilane, CAS number 2602-34-8.

[0056] Example Ten

[0057] The same as Example One, except that:

[0058] In this example, silane coupling agent number S10, specifically N-(hydroxyethyl)-N-methylaminopropyltrimethoxysilane, CAS number 330457-46-0.

[0059] Example Eleven

[0060] The same as Example One, except that:

[0061] In this example, silane coupling agent number S11, specifically 11-allyloxyundecyltrimethoxysilane, CAS number 1196453-35-6.

[0062] Example Twelve

[0063] The same as Example One, except that:

[0064] In this example, silane coupling agent number S12, specifically O-(propargyl)-N-(triethoxysilyl)carbamic acid methyl ester, CAS number 870987-68-1.

[0065] Example Thirteen

[0066] The same as Example One, except that:

[0067] In this example, silane coupling agent number S13, specifically 2-[methoxy(polyethyleneoxy)propyl]trimethoxysilane, CAS number 65994-07-2.

[0068] Example Fourteen

[0069] The same as Example One, except that:

[0070] In this example, silane coupling agent number S14, specifically O-[methoxy(polyethyleneoxy)]-N-(triethoxysilylpropyl)-carbamic acid ester, CAS number 65994-10-7.

[0071] Example Fifteen

[0072] The same as Example One, except that:

[0073] In this example, silane coupling agent number S15, specifically triethoxysilyl butyraldehyde, CAS number 917773-12-7 / 88276-92-0.

[0074] Comparative Example One

[0075] The same as Example One, except that:

[0076] In this example, no silane coupling agent is used, group number S0.

[0077] Comparative Example Two

[0078] The same as Example One, except that:

[0079] In this example, no filler is used, and no silane coupling agent is used, group number CK.

[0080] The examples 1-15 and comparative examples 1, 2 were tested for the relevant items, the test was carried out according to the provisions of GB / T 1040.3-2006, type 5 sample was used, and the sample was taken along the longitudinal direction of the sample. The test speed was 100±10 mm / min, and the gauge length was 25±0.25 mm. The results are shown in the following table.

[0081] As can be seen from the above table, the data of S1, S14 and S15 groups are better, and the elongation at break is greater than 150%. Among them, the silane coupling agent of S1 group has aldehyde group, the silane coupling agent of S14 group has urethane group, and the silane coupling agent of S15 group has aldehyde group. Therefore, it can be reasonably speculated that the glass flake treated with silane coupling agent having aldehyde group or urethane group has better dispersion effect in PVB resin, so that the elongation at break of PVB resin does not decrease significantly.

[0082] Example 16

[0083] The composition containing the filler comprises: 40 g of polyvinyl butyral resin PVB, 13.33 g of fatty alcohol polyoxyethylene ether Brij O10, and 1.65 g of fumed silica.

[0084] Among them, PVB is 18K26, which means that the molecular polymerization degree of PVB is about 1800, and the -OH content is about 26 wt%.

[0085] The fumed silica is pre-treated with a silane coupling agent.

[0086] The specific method is as follows: the fumed silica and the silane coupling agent are dispersed with toluene, heated to about 110°C, and kept for 6 h, and then solid-liquid separation is carried out by using a centrifuge, and the solid phase is baked at 85°C for 12 h.

[0087] In this example, the silane coupling agent is numbered S16, which is specifically 3-(trimethoxysilyl) methyl propyl methacrylate, and the CAS number is 2530-85-0.

[0088] The composition is heated to 90°C, vacuum stirring until completely compatible, and cast extrusion to obtain a PVB film with a thickness of 2 mm.

[0089] Example 17

[0090] The example 17 is basically the same as the example 16, except that:

[0091] In this example, the silane coupling agent is numbered S17, which is specifically O-(methacryloyloxyethyl)-N-(triethoxysilylpropyl) carbamate, and the CAS number is 115396-93-5.

[0092] Example 18

[0093] Example 19 is essentially the same as Example 16 except that:

[0094] In this example, silane coupling agent number S18 is specifically N-[5- (trimethoxysilylpropyl)-2-aza-1-oxopentyl]caprolactam, CAS number 106996-32-1.

[0095] Example 19

[0096] Example 19 is essentially the same as Example 16 except that:

[0097] In this example, silane coupling agent number S19 is specifically dihydro-3-[3- (triethoxysilyl)propyl]furan-2,5-dione, CAS number 93642-68-3.

[0098] Example 20

[0099] Example 20 is essentially the same as Example 16 except that:

[0100] In this example, silane coupling agent number S20 is specifically acetyloxypropyltrimethoxysilane, CAS number 59004-18-1.

[0101] Example 21

[0102] Example 21 is essentially the same as Example 16 except that:

[0103] In this example, silane coupling agent number S21 is specifically triethoxysilylpropyloxy(polyethyleneoxy)dodecanoate, CAS number 1041420-54-5.

[0104] Example 22

[0105] Example 22 is essentially the same as Example 16 except that:

[0106] In this example, silane coupling agent number S22 is specifically 3- isocyanatopropyltriethoxysilane, CAS number 24801-88-5.

[0107] Example 23

[0108] Example 23 is essentially the same as Example 16 except that:

[0109] In this example, silane coupling agent number S23 is specifically vinyltriethoxysilane, CAS number 78-08-0.

[0110] Example 24

[0111] Example 24 is essentially the same as Example 16 except that:

[0112] In this example, silane coupling agent No. S24, specifically, N-[3- (trimethoxysilyl)propyl]n-butylamine, CAS No. 31024-56-3.

[0113] Example Twenty-Five

[0114] Essentially the same as Example Sixteen, except that:

[0115] In this example, silane coupling agent No. S25, specifically, N-ethyl-3- trimethoxysilyl-2-methylpropylamine, CAS No. 227085-51-0.

[0116] Example Twenty-Six

[0117] Essentially the same as Example Sixteen, except that:

[0118] In this example, silane coupling agent No. S26, specifically, N-methyl-3- aminopropyltrimethoxysilane, CAS No. 3069-25-8.

[0119] Example Twenty-Seven

[0120] Essentially the same as Example Sixteen, except that:

[0121] In this example, silane coupling agent No. S27, specifically, N-[3- (triethoxysilyl)propyl]-4,5-dihydroimidazole, CAS No. 58068-97-6.

[0122] Example Twenty-Eight

[0123] Essentially the same as Example Sixteen, except that:

[0124] In this example, silane coupling agent No. S28, specifically, [3- (triethoxysilyl)propyl]ethylcarbamate, CAS No. 17945-05-0.

[0125] Comparative Example Three

[0126] Essentially the same as Example Sixteen, except that:

[0127] In this example, no silane coupling agent is used. Group No. S0.

[0128] Comparative Example Four

[0129] Essentially the same as Example Sixteen, except that:

[0130] In this example, no fumed silica is used, and no silane coupling agent is used. Group No. CK1.

[0131] Comparative Example Five

[0132] The present example is basically the same as Example Sixteen, except that:

[0133] In the present example, the silane coupling agent is replaced by diaminodiphenol DDS, and the group number is CK2.

[0134] Comparative Example Six

[0135] The present example is basically the same as Example Sixteen, except that:

[0136] In the present example, the silane coupling agent is replaced by polydimethylsiloxane PDMS, and the group number is CK3.

[0137] Some examples and comparative examples are tested for relevant items, and the test standard adopts T / CPIA 0015-2019, and the results are shown in the following table.

[0138] As can be seen from the above table, the tensile strength of S16, S23 and S24 groups is high, all above 32 MPa, and the elongation at break is also above 230%. The silane coupling agent of S16 group contains methacrylate group, the silane coupling agent of S23 group contains olefin group, and the silane coupling agent of S24 group has amino group, so it can be reasonably speculated that the silane coupling agent with methacrylate group, olefin group and amino group has better dispersion effect in PVB resin after surface treatment of fumed silica, so that the elongation at break of PVB resin does not decrease obviously, and its tensile strength is appropriately improved.

[0139] Although the tensile strength and elongation at break of Comparative Example Four meet the screening requirements, but it does not use fumed silica, so its adhesion to glass is obviously lower, only 60.80 N / cm. Comparative Example Six, CK3 group, is a common silicone oil PDMS treated fumed silica, compared with Comparative Example Four, it can be seen that the tensile strength is reduced, and the elongation at break is improved. That is, the surface treatment of fumed silica with silicone oil also has a certain effect, but due to the reduction of tensile strength, it does not meet the screening requirements.

[0140] Example Twenty-Nine

[0141] The composition containing the filler comprises: 80 g of polyvinyl butyral resin PVB, 23.9 g of fatty alcohol polyoxyethylene ether Brij O10, and 2.12 g of fumed silica.

[0142] Among them, PVB is 18K26, which means that the molecular polymerization degree of PVB is about 1800, and the -OH content is about 26 wt%.

[0143] The fumed silica is pre-treated with a silane coupling agent.

[0144] The specific treatment method is as follows: the fumed silica and the silane coupling agent are dispersed with toluene, heated to about 110°C, kept for 6h, then solid-liquid separation is performed by a centrifuge, and the solid phase is baked at 85°C for 12h.

[0145] In this embodiment, the silane coupling agent is numbered S16, specifically 3-(trimethoxysilyl) methyl propyl methacrylate, CAS number 2530-85-0.

[0146] The composition is heated to 90°C, vacuum stirring until completely compatible, and cast extruded to obtain a PVB film with a thickness of 0.8mm.

[0147] Example Thirty

[0148] The same as example twenty-nine, except that:

[0149] The amount of Brij O10 used is 11.94g, and the amount of fumed silica is 1.06g.

[0150] Among them, PVB is 18K37. The fumed silica is also pre-treated with a silane coupling agent.

[0151] The specific treatment method is as follows: the fumed silica and the silane coupling agent are dispersed with toluene, heated to about 110°C, kept for 6h, then solid-liquid separation is performed by a centrifuge, and the solid phase is baked at 85°C for 12h.

[0152] In this embodiment, the silane coupling agent is numbered S16, specifically 3-(trimethoxysilyl) methyl propyl methacrylate, CAS number 2530-85-0.

[0153] The composition is heated to 90°C, vacuum stirring until completely compatible, and cast extruded to obtain a PVB film with a thickness of 0.8mm.

[0154] Examples twenty-nine, thirty are tested for relevant items, and the test standard adopts T / CPIA 0015-2019, and the results are shown in the following table.

[0155] As can be seen from the above table, the -OH content of PVB and the addition amount of fumed silica have important influence on tensile strength, elongation at break, bonding strength to glass, light transmittance, light attenuation and other parameters.

Claims

1. A composition comprising a filler, characterized in that: The transparent filler is surface treated by silane coupling agent, and is glass flake, glass powder, glass fiber, transparent montmorillonite, transparent mica, fumed silica, amorphous silica, quartz sand, quartz powder, nano-silica, zeolite, transparent alumina ceramic, transparent magnesia ceramic, transparent yttrium ceramic, transparent aluminum-magnesia spinel ceramic, transparent aluminum nitride ceramic, transparent aluminum oxynitride ceramic, transparent PLZT electro-optic ceramic, transparent yttrium-aluminum garnet laser ceramic, and transparent scintillation ceramic.

2. The composition comprising a filler according to claim 1, characterized in that: The amount of the transparent filler is not more than 40wt% of the total amount.

3. The composition comprising filler according to claim 2, characterized in that: The silane coupling agent is a silane coupling agent with active groups selected from one of amino group, aldehyde group, olefin group, and carbamate group.

4. The composition comprising filler according to claim 2, characterized in that: The surface treatment is that the transparent filler and the silane coupling agent are dispersed into an organic solvent, heated for 1-10 hours, then solid-liquid separated and dried.

5. The composition comprising filler according to claim 1, characterized in that: ​

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