CN111825830B - Modified phytic acid derivative resin, light-curable liquid flame-retardant resin and flame-retardant film and preparation method thereof - Google Patents
Modified phytic acid derivative resin, light-curable liquid flame-retardant resin and flame-retardant film and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C09J2463/00—Presence of epoxy resin
- C09J2463/006—Presence of epoxy resin in the substrate
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- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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Abstract
The invention provides a modified phytic acid derivative resin, which comprises a reaction product of the following components: 35 to 65wt.% of phytic acid, 20 to 65wt.% of an epoxy compound having a double bond, and 0 to 35wt.% of a bifunctional epoxy compound, based on the total weight of the modified phytic acid derivative resin as 100 wt.%. The present invention also provides a photocurable liquid flame-retardant resin comprising, based on 100wt.% of the total weight of the liquid flame-retardant resin: 79 to 99.9wt.% of the modified phytic acid derivative resin; 0-20wt.% of a urethane acrylate resin; and 0.1 to 5wt.% of a photoinitiator. And curing the liquid flame-retardant resin to obtain the flame-retardant film, wherein the flame-retardant film has good flame-retardant property and good mechanical property.
Description
Technical Field
The invention relates to modified phytic acid derivative resin, liquid flame-retardant resin and a flame-retardant film, in particular to light-curable liquid flame-retardant resin and a flame-retardant film and preparation methods thereof.
Background
The flame-retardant material plays an important role in social safety production and life. In recent years, a plurality of industry standards are issued by the nation to strengthen the application of flame retardant materials in various fields. The halogen-containing flame retardant which is widely used before is gradually limited in use due to the environmental protection, so that the halogen-free flame retardant is more favored by the majority of users. Most halogen-free flame retardants have lower flame retardant efficiency than halogen-containing flame retardants. Meanwhile, the thin film, the adhesive tape and other products with small thickness have stronger combustibility, and the flame retardance of UL-94VTM0 grade is difficult to achieve by adopting the halogen-free flame retardant. If too much flame retardant is added, the properties of the material itself, such as strength, tackiness, etc., will be greatly affected.
The organic phosphorus flame retardant has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, accords with the development direction of the flame retardant, and has good development prospect.
The organic phosphorus flame retardants are of various types, and are classified into additive flame retardants and reactive flame retardants according to the method of use. Chinese patent application CN201010123312.3 (Xia Yuzheng and the like) discloses a preparation method of a combined phosphorus type flame-retardant acrylate pressure-sensitive adhesive. The preparation method is characterized in that the preparation of the flame-retardant pressure-sensitive adhesive is carried out by adopting a flame retardant and a flame-retardant system which are universal, easy to obtain, low in price and environment-friendly; the pressure-sensitive adhesive with excellent pressure-sensitive property and flame retardance can be obtained by copolymerizing a phosphorus-containing acrylate monomer with a conventional acrylate monomer and introducing a phosphate group to endow the acrylate pressure-sensitive adhesive with flame retardance, so that the intrinsic flame-retardant high-molecular pressure-sensitive adhesive is prepared, and then a small amount of flame retardant is added.
Phytic acid has a high phosphorus content, so that phytic acid or its derivatives have been used in halogen-free flame retardant products. US2006234044 (NAKANISHI TORU, etc.) discloses a two-component flame retardant adhesive, which comprises (a) a non-halogen based epoxy resin, (B) a thermoplastic resin and/or a synthetic rubber, (C) a curing agent, (D) a phytate compound, and (E) a curing accelerator. The adhesive can be used for adhering sheets, covering films and flexible copper laminated plates.
JP5311380 (TAGUCHI KAZHUHIRO, etc.) discloses a flame retardant epoxy resin and a preparation method thereof. The phosphorus-containing flame retardant epoxy resin comprises an epoxy compound, an alcohol and a phosphorus-containing phytic acid. Under the catalysis of acid, the epoxy compound and phytic acid undergo cationic polymerization.
Disclosure of Invention
The invention aims to provide a modified phytic acid derivative resin, a light-curable liquid flame-retardant resin is prepared by utilizing the modified phytic acid derivative resin, a flame-retardant film obtained by light curing of the liquid flame-retardant resin does not contain halogen, and the flame-retardant grade can reach UL-94V-0.
According to one aspect of the present invention, there is provided a modified phytic acid derivative resin comprising a reaction product of: 35 to 65wt.% of phytic acid, 20 to 65wt.% of an epoxy compound having a double bond, and 0 to 35wt.% of a bifunctional epoxy compound, based on the total weight of the modified phytic acid derivative resin as 100 wt.%.
According to certain embodiments of the present invention, the double bond-containing epoxy compound is selected from one or more of the following: glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ester.
According to certain embodiments of the present invention, the phytic acid is present in an amount of 45 to 55wt.%, based on the total weight of the modified phytic acid derivative resin being 100 wt.%.
According to certain embodiments of the present invention, the double bond-containing epoxy compound is present in an amount of 30 to 40wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
According to certain embodiments of the present invention, the bifunctional epoxy compound is present in an amount of 10 to 20wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
According to another aspect of the present invention, there is provided a photocurable liquid flame-retardant resin comprising, in 100wt.% based on the total weight of the liquid flame-retardant resin: 79 to 99.9wt.% of the modified phytic acid derivative resin as described above; 0-20wt.% of a urethane acrylate resin; and 0.1 to 5wt.% of a photoinitiator.
According to certain embodiments of the present invention, the modified phytic acid derivative resin content is 82 to 87wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
According to certain embodiments of the present invention, the urethane acrylate resin is present in an amount of 12 to 17wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
According to certain embodiments of the present invention, the photoinitiator is present in an amount of 0.1 to 1wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
According to certain embodiments of the present invention, the resin composition further comprises 0 to 30wt.% of expandable graphite, based on 100wt.% of the total weight of the liquid flame retardant resin.
According to certain embodiments of the present invention, the expandable graphite is present in an amount of 5 to 10wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
According to another aspect of the present invention, the present invention provides a flame retardant film, which is formed by photo-curing a liquid film made of the liquid flame retardant resin.
According to another aspect of the present invention, the present invention provides a flame retardant adhesive tape formed by bonding the flame retardant film as a substrate to an adhesive film.
According to some embodiments of the present invention, the adhesive film attached to the substrate is a pressure-sensitive adhesive film, a heat-sensitive adhesive film, a photo-curable adhesive film or a moisture-curable adhesive film.
Detailed Description
It is to be understood that other various embodiments can be devised and modifications can be made by those skilled in the art based on the teachings of this specification without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing quantities and physical and chemical properties used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that can be calculated by those skilled in the art utilizing the teachings disclosed herein to achieve the desired properties, and the appropriate changes to these approximations. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1, 2, 3, 4, and 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
Modified phytic acid derivative resin
The modified phytic acid derivative resin provided by the invention is a reaction product comprising the following components: 35 to 65wt.% of phytic acid, 20 to 65wt.% of epoxy compound containing double bonds, and 0 to 35wt.% of bifunctional epoxy compound, based on 100wt.% of the modified phytic acid derivative resin, the phytic acid used is an aqueous solution with a concentration of 30wt.% or more, preferably 50wt.% or more, the weight percent of the phytic acid in the modified phytic acid derivative resin is calculated based on the weight of pure phytic acid, when the phytic acid content is less than 35wt.%, the flame retardant film prepared is not good in flame retardant effect, when the phytic acid content is more than 65wt.%, the light curing of the flame retardant resin is incomplete, the phytic acid content is preferably 45 to 55wt.%, based on 100wt.% of the modified phytic acid derivative resin, within the range, the flame retardant film prepared has better flame retardant property, and the mechanical properties of the flame retardant film can be simultaneously considered; the double bond-containing epoxy compound is preferably glycidyl methacrylate, glycidyl acrylate and/or allyl glycidyl ester, more preferably glycidyl methacrylate, the double bond-containing epoxy compound is contained in an amount of 20 to 65wt.%, preferably 30 to 40wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin, the obtained liquid flame retardant resin is not completely cured when the double bond-containing epoxy compound is contained in an amount of less than 20wt.%, and the flame retardant film is less effective when the double bond-containing epoxy compound is contained in an amount of more than 65 wt.%.
Photocurable liquid flame retardant resin
The light-curable liquid flame-retardant resin provided by the invention is a reaction product comprising the following components:
79 to 99.9wt.% of modified phytic acid derivative resin, 0 to 20wt.% of urethane acrylate resin, and 0.1 to 5wt.% of photoinitiator, based on 100wt.% of the total weight of the liquid flame retardant resin.
The content of the modified phytic acid derivative resin is preferably 82-87wt.%, based on 100wt.% of the total weight of the liquid flame-retardant resin, when the content of the modified phytic acid derivative resin is less than 79wt.%, the flame-retardant film prepared has poor flame-retardant performance, when the content of the modified phytic acid derivative resin is more than 99.9wt.%, enough photoinitiator cannot be added, so that the photocured liquid flame-retardant resin cannot be obtained, and when the content of the modified phytic acid derivative resin is 82-87wt.%, the flame-retardant film obtained has good flame-retardant performance and good mechanical properties. The urethane acrylate resin can be any urethane resin containing an acryloyl functional group, and when the content of the urethane acrylate resin is preferably 12-17wt.%, the mechanical properties of the prepared flame-retardant film are better. The photoinitiator is any compound which generates free radicals after illumination to initiate monomer polymerization, and can be selected from a UV photoinitiator or a visible photoinitiator, the content of the photoinitiator is preferably 0.1-1wt.%, and the total weight of the liquid flame-retardant resin is 100wt.%, and the prepared flame-retardant film is completely cured.
The liquid flame retardant resin may further include 0 to 30wt.% of expandable graphite, based on 100wt.% of the total weight of the liquid flame retardant resin, the flame retardant performance of the flame retardant film may be further improved, the expandable graphite is preferably included in an amount of 5 to 10wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin, when the expandable graphite is included in an amount of more than 30wt.%, the mechanical properties of the flame retardant film may be poor, and the mesh number of the expandable graphite is preferably 50 to 500 mesh.
Flame-retardant film, flame-retardant adhesive tape and preparation method thereof
The 'photocurable liquid flame-retardant resin' is applied on a base material, and then photocured in an oxygen-isolated environment to form a flame-retardant film. The method comprises the following steps of (1) applying light-curable liquid flame-retardant resin between two release films, and tearing off the release films on two sides after photocuring to obtain the flame-retardant film; alternatively, the "photocurable liquid flame retardant resin" is applied on a release film and then photocured in an oxygen-free environment, and the application may be by coating, and the coating method may preferably be one or more of the following: roll coating, flow coating, dip coating, spin coating, spray coating, blade coating, and die coating. The flame retardant film may be formed to a thickness of 100 to 5000 microns, preferably 200 to 2000 microns, more preferably 500 to 1000 microns. The light for curing may be UV lamp, visible light, etc., and its energy density may be 10mJ/cm 2 Above, preferably 300-1000mJ/cm 2 。
The flame-retardant film is used as a base material and is jointed with an adhesive film to form the flame-retardant adhesive tape. The adhesive film attached to the base material can be a pressure-sensitive adhesive film, a heat-sensitive adhesive film, a photo-curing adhesive film, a moisture-curing adhesive film and the like, the adhesive film is made of any material, such as polyacrylate, rubber, polyurethane, silica gel and the like, and in addition, the thickness of the adhesive film attached to the base material needs to be adjusted according to the requirements of the flame retardance and the viscosity of practical application and the flame retardance and the thickness of the compounded flame-retardant film provided by the invention. The bonding mode of the base material and the adhesive film can be single-side bonding or double-side bonding, and correspondingly, a single-side flame-retardant adhesive tape and a double-side flame-retardant adhesive tape can be prepared.
The flame-retardant film and the flame-retardant adhesive tape have good flame-retardant performance, and the formula can be adjusted according to requirements so that the flame-retardant film and the flame-retardant adhesive tape have good flame-retardant performance and good mechanical performance simultaneously
The present invention provides various preferred embodiments regarding a liquid flame retardant resin, a flame retardant film and a flame retardant adhesive tape thereof.
Preferred embodiment 1 is a modified phytic acid derivative resin comprising a reaction product of: 35-65wt.% phytic acid, 20-65wt.% of an epoxy compound having a double bond, and 0-35wt.% of a bifunctional epoxy compound, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
Preferred embodiment 2 is the modified phytic acid derivative resin according to preferred embodiment 1, wherein the double-bond-containing epoxy compound is one or more selected from the group consisting of: glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ester.
Preferred embodiment 3 is the modified phytic acid derivative resin according to preferred embodiment 1, wherein the phytic acid is present in an amount of 45 to 55wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
Preferred embodiment 4 is the modified phytic acid derivative resin according to preferred embodiment 1, wherein the double bond-containing epoxy compound is present in an amount of 30 to 40wt.%, based on 100wt.% based on the total weight of the modified phytic acid derivative resin.
Preferred embodiment 5 is the modified phytic acid derivative resin according to preferred embodiment 1, wherein the bifunctional epoxy compound is present in an amount of 10 to 20wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
Preferred embodiment 6 is a photocurable liquid flame-retardant resin comprising, based on 100wt.% of the total weight of the liquid flame-retardant resin:
79 to 99.9wt.% of the modified phytic acid derivative resin;
0-20wt.% of a urethane acrylate resin; and
0.1-5wt.% of a photoinitiator.
Preferred embodiment 7 is the liquid flame retardant resin of preferred embodiment 6, wherein the modified phytic acid derivative resin is present in an amount of 82 to 87wt.%, based on the total weight of the liquid flame retardant resin, of 100 wt.%.
Preferred embodiment 8 is the liquid flame retardant resin of preferred embodiment 6, wherein the urethane acrylate resin is present in an amount of 12 to 17wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
Preferred embodiment 9 is the liquid flame retardant resin of preferred embodiment 6, wherein the photoinitiator is present in an amount of 0.1 to 1wt.%.
Preferred embodiment 10 is a liquid flame retardant resin as described in preferred embodiment 6, further comprising 0 to 30wt.% expandable graphite, based on 100wt.% of the total weight of the liquid flame retardant resin.
Preferred embodiment 11 is the liquid flame retardant resin of preferred embodiment 6, wherein the expandable graphite is present in an amount of 5 to 10wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
Preferred embodiment 12 is a flame-retardant film formed by photocuring a liquid film made of the liquid flame-retardant resin according to any one of preferred embodiments 6 to 11.
Preferred embodiment 13 is a flame retardant adhesive tape formed by bonding a flame retardant film according to preferred embodiment 11 as a base material and an adhesive film.
Preferred embodiment 14 is the flame retardant adhesive tape according to preferred embodiment 13, wherein the adhesive film attached to the substrate is a pressure-sensitive adhesive film, a heat-sensitive adhesive film, a photo-curable adhesive film or a moisture-curable adhesive film.
The following examples and comparative examples are provided to aid in the understanding of the present invention and should not be construed as limiting the scope of the invention. All parts and percentages are by weight unless otherwise indicated.
The raw materials used in the examples of the present invention and the comparative examples are shown in table 1 below.
TABLE 1 raw materials used in examples and comparative examples
The adhesiveness of the flame retardant tapes provided in examples and comparative examples was evaluated mainly by a 180-degree peel force test, the flame retardant properties of the flame retardant films and flame retardant tapes provided in examples and comparative examples were evaluated by a flame retardant test, and the mechanical properties of the flame retardant films and flame retardant tapes provided in examples and comparative examples were further evaluated by tensile stress and elongation at break tests.
180 degree peel force test
The 180 degree room temperature peel force test procedure is described in ASTM International Standard D3330. The test is completed on an Instron tensile tester, the peeling speed is 304.8mm/min, the used adhered base material is a standard steel plate, and the sample preparation method is that a 25.4mm multiplied by 200mm adhesive tape sample is rolled back and forth by a 1kg rubber roller to be adhered to the surface of the steel plate once, and the prepared sample to be tested is placed for 20min in an environment with 23 ℃ and 60% relative humidity and then is tested. The number of samples representing the same performance should not be less than five, and the test results are expressed as the arithmetic mean of the peel strengths in N/mm. The test result of the adhesiveness can provide reference for a user to select a proper flame-retardant resin according to the application requirement.
The test results of 180 degree peel force of the flame retardant adhesive tapes provided in the examples of the present invention and comparative examples are shown in table 4.
Flame retardancy test
According to the UL-94 (standard established by underwriters Laboratories, u.s.underwritrs' Laboratories inc.) vertical burning test, a flame was placed under the sample for 10 seconds and then removed, and the time taken for the sample to stop burning was measured. Two sets of samples were evaluated, 5 samples each (10 total burn times measured). The maximum burn time of the 10 burn times, the sum of the 10 burn times and the presence or absence of droplets during the burn were evaluated. The rating of the flame retardancy classification is given below. Other details are in accordance with the UL-94 standard.
V-0: maximum burning time, 10 seconds or less; total burn time, 50 seconds or less; no droplets were present.
V-1: maximum burn time, 30 seconds or less; total burn time, 250 seconds or less; no droplets were present.
V-2: maximum burn time, 30 seconds or less; total burn time, 250 seconds or less; droplets are present.
And (3) combustion: the above condition is not satisfied.
In the invention, the general flame retardant requirement can be met through the test of UL-94V-2, and the higher flame retardant requirement can be met through the test of UL-94V-0.
The test results of the flame retardancy of the flame retardant films provided in the examples and comparative examples of the present invention are listed in table 3, and the test results of the flame retardancy of the flame retardant tapes provided in the examples and comparative examples of the present invention are listed in table 4.
Tensile stress and elongation at break test
The test was carried out on an Instron tensile tester at a tensile speed of 12.7mm/min and a distance of 100mm between the upper and lower grips. The sample preparation method comprises cutting the sample into 25.4mm × 200mm, standing the prepared sample to be tested at 23 deg.C and 60% relative humidity for 20min, and testing. The number of samples representing the same property should not be less than five, the ratio of the maximum stress to the cross-sectional area of the pattern is tensile stress in MPa, and the elongation at break of the pattern is the elongation at break. The test results of the tensile stress and the elongation at break can provide reference for a user to select proper flame-retardant resin according to the application requirement of the user.
The tensile stress and elongation at break test results of the flame retardant films provided in the examples of the present invention and the comparative examples are shown in table 3.
Preparation of modified phytic acid derivative resin
Examples E1-1 to E1-8 and CE1-9
In an ice-water bath at 0 ℃, an epoxy compound containing double bonds and a bifunctional epoxy compound are slowly added to phytic acid (50% aqueous solution) while stirring. The reaction generates a large amount of heat, and the rate of addition is controlled to maintain the reaction temperature at 60 ℃. After the epoxy group is completely reacted, the temperature is gradually returned to the room temperature, and the viscosity of the solution is increased to obtain the modified phytic acid derivative resin. The amounts of phytic acid (50% aqueous solution), double bond-containing epoxy compound and bifunctional epoxy compound added are shown in Table 2.
TABLE 2 formulation of modified phytic acid derivative resin in examples and comparative examples
Preparation and performance test of light-curable liquid flame-retardant resin and flame-retardant film
Examples E2-1 to E2-13, and CE2-14 to CE2-15
Adding urethane acrylate and a photoinitiator Ingracure184 into the modified phytic acid derivative resin, and uniformly stirring to obtain the light-curable liquid flame-retardant resin. The resin was coated between two release films with a comma roll, and cured under a UV lamp (energy density 500 mJ/cm) with a slit of 500 μm 2 10 seconds). And tearing off the two-sided release film to obtain the light-curable flame-retardant film. The amounts of the modified phytic acid derivative resin, urethane acrylate and photoinitiator Ingracure184 added are referred to table 3.
Examples CE2 to 16
20g of urethane acrylate and 0.3g of photoinitiator Ingracure184 were added to 80g of phytic acid, and after stirring and standing for 5 minutes, the mixture was layered and a photocurable liquid flame-retardant resin could not be obtained.
As can be seen from Table 3, the flame retardant rating of the flame retardant film obtained after curing in examples E2-1 to E2-13 can reach more than UL-94V-1, so that the flame retardant film has good flame retardant property; the flame-retardant films obtained after curing in examples E2-4 to E2-13 have better tensile stress and elongation at break. Examples E2-1 to E2-3 are flame retardant films obtained from pure modified phytic acid derivative resins, and thus have good flame retardant properties, but have poor tensile stress and elongation at break; examples E2-4 to E2-13 are flame retardant films obtained after curing modified phytic acid derivative resins to which a certain amount of urethane acrylic resin was added, the tensile stress and elongation at break of which were increased more as the amount of the urethane acrylic resin was increased, but when the amount of the urethane acrylic resin was too large as CE2-15, the mass percentage (P%) of total phosphorus in the resins was too low, resulting in poor flame retardant properties of the obtained flame retardant films. In examples E2-4 to E2-13, the flame retardant film obtained after curing had good flame retardant properties, as well as good mechanical properties such as tensile stress and elongation at break. In examples E2-4, E2-6, and E2-8 to E2-13, the total phosphorus content (P%) in the resin was about 6.0% or more, and the flame retardant film obtained after curing had better flame retardant properties.
Preparation and Performance testing of flame-retardant adhesive tapes
Examples E3-1 to E3-6
Photocurable liquid flame-retardant resins prepared according to examples E2-9 were further mixed with expandable graphite and homogenized according to Table 4, and the resins were coated between two release films with a comma roller having a slit width of 500 μm and cured under a UV lamp (energy density of 500 mJ/cm) 2 10 seconds). Tearing the release film from both sidesTo obtain the light-curable flame-retardant film. And (3M) pressure-sensitive adhesive films with different thicknesses and brands are stuck on two sides of the flame-retardant film to obtain the flame-retardant double-sided adhesive tape. The thickness and the number of the 3M pressure-sensitive adhesive film are shown in Table 4.
Examples E3-7 to E3-8
A photocurable liquid flame-retardant resin was prepared according to examples E2 to E9, and after 5% by weight of expandable graphite was further added according to Table 4 and stirred uniformly, the resin was foamed with nitrogen gas, coated between two release films with a comma roller, with a slit width of 500 μm, and cured under a UV lamp (energy density 500 mJ/cm) 2 10 seconds). And tearing off the two-sided release film to obtain the photocurable flame-retardant foaming film with the thickness of 500 micrometers. And (3M) pressure-sensitive adhesive films with different thicknesses and brands are stuck on two sides of the flame-retardant film to obtain the flame-retardant double-sided adhesive tape. The thickness and the number of the 3M pressure-sensitive adhesive film are shown in Table 4.
TABLE 4 formulation and corresponding Performance parameters of the flame retardant adhesive tapes in the examples and comparative examples
Note that EG in Table 4 represents expandable graphite
As can be seen from Table 4, examples E3-1 and E3-3 are flame retardant double-sided tapes obtained by pasting a pressure sensitive adhesive film with a certain thickness on both sides of a flame retardant film, and the flame retardant grade of the flame retardant double-sided tapes is UL-94V-1, which is lower than that of the corresponding flame retardant film, but still has better flame retardant property. As can also be seen from Table 4, all of the flame retardant tapes prepared in examples F3-1 to E3-8 had 180 degree peel forces of not less than 0.5N/mm and thus had good adhesiveness. Examples E3-2, E3-4 to E3-8 are double-sided adhesive tapes prepared by further adding 5% by weight of expandable graphite to a liquid flame-retardant resin, and when the thickness of the pressure-sensitive adhesive film is not more than about 30 μm, the flame-retardant rating of the double-sided adhesive tape can be increased to UL-94V-0, and at the same time, the prepared double-sided adhesive tape has good adhesiveness.
Although the foregoing detailed description contains many specific details for the purpose of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, alterations, substitutions and alterations to these details are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitation on the invention as claimed. The proper scope of the invention should be determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.
Claims (14)
1. A modified phytic acid derivative resin comprising the reaction product of: 35 to 65wt.% of phytic acid, 20 to 65wt.% of an epoxy compound having a double bond, and 0 to 35wt.% of a bifunctional epoxy compound, based on the total weight of the modified phytic acid derivative resin as 100 wt.%.
2. The modified phytic acid derivative resin according to claim 1, wherein the double bond-containing epoxy compound is one or more selected from the group consisting of: glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ester.
3. The modified phytic acid derivative resin of claim 1, wherein the phytic acid is present in an amount of 45 to 55wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
4. The modified phytic acid derivative resin according to claim 1, wherein the double bond-containing epoxy compound is present in an amount of 30 to 40wt.%, based on 100wt.% based on the total weight of the modified phytic acid derivative resin.
5. The modified phytic acid derivative resin according to claim 1, wherein the bifunctional epoxy compound is present in an amount of 10 to 20wt.%, based on 100wt.% of the total weight of the modified phytic acid derivative resin.
6. A photocurable liquid flame-retardant resin comprising, in 100wt.% based on the total weight of the liquid flame-retardant resin:
79 to 99.9wt.% of the modified phytic acid derivative resin of any of claims 1 to 5;
0-20wt.% of a urethane acrylate resin; and
0.1-5wt.% of a photoinitiator.
7. A liquid flame retardant resin according to claim 6, wherein the modified phytic acid derivative resin is present in an amount of 82 to 87wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
8. A liquid flame retardant resin according to claim 6, wherein said urethane acrylate resin is present in an amount of 12 to 17wt.%, based on 100wt.% of the total weight of said liquid flame retardant resin.
9. A liquid flame retardant resin according to claim 6, wherein the photoinitiator is present in an amount of 0.1 to 1wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
10. The liquid flame retardant resin of claim 6, further comprising 0-30wt.% expandable graphite, based on 100wt.% of the total weight of the liquid flame retardant resin.
11. A liquid flame retardant resin according to claim 10, wherein the expandable graphite is present in an amount of 5 to 10wt.%, based on 100wt.% of the total weight of the liquid flame retardant resin.
12. A flame-retardant film formed by photocuring a liquid film made of the liquid flame-retardant resin according to any one of claims 6 to 11.
13. A flame-retardant adhesive tape comprising the flame-retardant film according to claim 12 as a base material and an adhesive film laminated thereto.
14. The flame retardant adhesive tape according to claim 13, wherein the adhesive film attached to the substrate is a pressure-sensitive adhesive film, a heat-sensitive adhesive film, a photo-curable adhesive film or a moisture-curable adhesive film.
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| CN201910331420.0A CN111825830B (en) | 2019-04-23 | 2019-04-23 | Modified phytic acid derivative resin, light-curable liquid flame-retardant resin and flame-retardant film and preparation method thereof |
| PCT/IB2020/053095 WO2020217120A1 (en) | 2019-04-23 | 2020-04-01 | Modified phytic acid derivative resin, light-curable liquid flame-retardant resin, flame-retardant film and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006037027A (en) * | 2004-07-30 | 2006-02-09 | Kansai Paint Co Ltd | Aqueous resin composition |
| JP2010070695A (en) * | 2008-09-22 | 2010-04-02 | National Institute Of Advanced Industrial Science & Technology | Flame-retardant epoxy resin and method for producing the same |
| JP2011079950A (en) * | 2009-10-07 | 2011-04-21 | Toyo Ink Mfg Co Ltd | Flame-retardant resin composition |
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| KR20060108507A (en) * | 2005-04-13 | 2006-10-18 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same |
| CN104264467B (en) * | 2014-09-15 | 2016-08-31 | 河南工程学院 | A kind of preparation method of flame-proof cotton fabric |
| CN108342906B (en) * | 2017-04-19 | 2020-05-26 | 安徽工程大学 | Down-based composite material, preparation method and application thereof |
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| JP2006037027A (en) * | 2004-07-30 | 2006-02-09 | Kansai Paint Co Ltd | Aqueous resin composition |
| JP2010070695A (en) * | 2008-09-22 | 2010-04-02 | National Institute Of Advanced Industrial Science & Technology | Flame-retardant epoxy resin and method for producing the same |
| JP2011079950A (en) * | 2009-10-07 | 2011-04-21 | Toyo Ink Mfg Co Ltd | Flame-retardant resin composition |
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| 含环氧基团三元共聚物纳米纤维的植酸改性;刘新华等;《高分子材料科学与工程》;20170630;第33卷(第6期);第135-139页 * |
| 基于植酸改性的羽毛吸附材料的制备及其性能;刘新华等;《功能高分子学报》;20170930;第30卷(第3期);第354-359页 * |
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