CN109694450A - A kind of sun-proof film forming polymer and preparation method thereof - Google Patents
A kind of sun-proof film forming polymer and preparation method thereof Download PDFInfo
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- CN109694450A CN109694450A CN201910049768.0A CN201910049768A CN109694450A CN 109694450 A CN109694450 A CN 109694450A CN 201910049768 A CN201910049768 A CN 201910049768A CN 109694450 A CN109694450 A CN 109694450A
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- Prior art keywords
- methyl
- film forming
- sun
- proof film
- forming polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/91—Graft copolymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Abstract
The invention discloses a kind of sun-proof film forming polymers, are obtained by following monomer by emulsion polymerization: accounting at least one carboxylic acid monomer of total monomer weight 15-25wt%；Account for the acrylamide derivative of at least one structure shown in formula I of total monomer weight 30-60wt%:R1With R2For hydrogen or C4‑C12Alkyl, but R1With R2It is not simultaneously hydrogen；Account for (methyl) acrylic acid C1-C4 Arrcostab of total monomer weight 15-30wt%；Account for (methyl) acrylic acid C12-C18 Arrcostab of total monomer weight 3-10wt%；Account for single sealing end of total monomer weight 5-10wt% or the vinyl silicone oil of bi-end-blocking.The present invention relates to polymeric material fields, the polymer, which is used to can provide excellent water resistant when sunscreen cosmetic, washes ability, it can be used for ethanol system formula, it can be used for aqueous systems formula, the polymer can provide emulsifying capacity simultaneously in aqueous systems formula, grease and oiliness active matter in emulsifiable and stabilized formulations.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of sun-proof film forming polymer and preparation method thereof.
Background technique
With the improvement of living standards, people are also increasingly stronger to the consciousness for protecting the skin from uv damage.Investigation
It has been shown that, demand of the consumer to sunscreen cosmetic increase year by year, wherein high spf value and the sunscreen cosmetic of high PA value increasingly by
To everybody welcome.But the sunscreen product only with high spf value and high PA value is no longer satisfied the demand of people.
With the change of consumer perceptions, people increasingly pay close attention to the anti-friction performance of waterproof of sunscreen cosmetic, more pleasant skin sense and make
Convenience.Especially for outdoor sports and like for the crowd of aquatic sports, there is high SPF and excellent
The aerial fog type product of the anti-sweat function of waterproof is just more able to satisfy demand.However, the overwhelming majority has the product of water-proof function on the market
It is all oiliness formula, it usually all can be poor to a kind of wax of user and greasy feeling, usage experience.
In order to make sunscreen cosmetic have waterproofness, polymer would generally be added as film forming in present people in cosmetics
Agent.But existing film former polymer product or be that waterproof performance is bad or be exactly water-soluble or alcohol-soluble is bad
Cause to be not applied for aqueous systems and alcohol system.
Patent US5204090 discloses the light screening composition containing water-insoluble film forming polymer.The patent is used
Film forming agent be a kind of acrylate copolymer, when the moisturizing rouge of itself and trade name Arlamol E are used in conjunction with have compared with
Good sun-proof performance and waterproof performance.
Patent US5653965 discloses a kind of film forming polymer for sunscreen spray, which is methyl ethylene
Ether and butyl maleate copolymer.The polymer is mainly used in the sunscreen of aerosol type in that patent, does not refer to that it is anti-
Aqueous energy.
Patent US4663157 discloses a kind of sunscreen cosmetic of scratch-resistant.Ethylene/acrylic acid is disclosed in that patent
Copolymer.It can have the effect that scratch resistant scrape along stablizes sun-proof ability using the polymer in sunscreen product.
Patent CN100536821C, which is disclosed, uses acrylate copolymer emulsion as waterproofing agent in personal care articles
Application.The acrylate copolymer has excellent waterproof performance, but does not refer to it in the sunscreen spray of ethanol system
Using.
Patent CN102186452A discloses a kind of terpolymer for ultra light sun block lotion.The copolymer can be such that product has
There are better water resistance and sun-proof result, but does not refer to its application in the sunscreen spray of ethanol system.
Summary of the invention
The purpose of the present invention is to provide a kind of sun-proof film forming polymer, which is used to can provide when sunscreen cosmetic
Excellent water resistant washes ability, can be used for ethanol system formula, can be used for aqueous systems formula, the polymerization in aqueous systems formula
Object can provide emulsifying capacity simultaneously, grease and oiliness active matter in emulsifiable and stabilized formulations.
To achieve the goals above, present invention provide the technical scheme that a kind of sun-proof film forming polymer, by following monomer
It is obtained by emulsion polymerization:
Account at least one carboxylic acid monomer of total monomer weight 15-25wt%；
Account for the acrylamide derivative of at least one structure shown in formula I of total monomer weight 30-60wt%:
R1With R2For hydrogen or C4-C12Alkyl, but R1With R2It is not simultaneously hydrogen；
Account for (methyl) acrylic acid C1-C4 Arrcostab of total monomer weight 15-30wt%；
Account for (methyl) acrylic acid C12-C18 Arrcostab of total monomer weight 3-10wt%；
Account for single sealing end of total monomer weight 5-10wt% or the vinyl silicone oil of bi-end-blocking.
In above-mentioned sun-proof film forming polymer, the carboxylic acid monomer be selected from acrylic acid, methacrylic acid, itaconic acid,
One of fumaric acid, crotonic acid, maleic acid are a variety of.
In above-mentioned sun-proof film forming polymer, acrylamide derivative described in the Formulas I is N- tert-butyl acryloyl
Amine, N- t-octyl acrylamide, N, N- dioctyl acrylamide, N, one or more of N- dodecyl acrylamide.
In above-mentioned sun-proof film forming polymer, (methyl) the acrylic acid C1-C4Arrcostab is (methyl) acrylic acid first
Ester, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,
One or more of (methyl) propyl acrylate.
In above-mentioned sun-proof film forming polymer, the vinyl silicone oil of single sealing end or bi-end-blocking, viscosity exists
Within 1000mPas.
In above-mentioned sun-proof film forming polymer, (methyl) the acrylic acid C12-C18Arrcostab is lauryl
It is ester, octadecyl methacrylate, tridecyl acrylate, one or more in methacrylic acid cetyl ester.
Meanwhile the invention also discloses the preparation method of a kind of as above any sun-proof film forming polymer, features
It is, includes the following steps:
Step 1: monomer and ethyl alcohol being added in first reactor, stirring is opened and is mixed, be configured to monomer solution；
Step 2: all or part of initiator being added in ethyl alcohol, initiator solution is configured to；
Step 3: ethyl alcohol being added in second reactor, leads to nitrogen, stirs and be warming up to 50-90 DEG C；
Step 4: after second reactor is warming up to required temperature, partial monosomy solution and part initiator solution is added,
Start while being added monomer solution and initiator solution after a period of time, time for adding is 3-10 hours；
Step 5: after initiator and monomer solution are added dropwise to complete, continue held for some time, be down to room temperature after heat preservation,
Obtain polymer solution.
Further include step 6 in the preparation method of above-mentioned sun-proof film forming polymer: the polymer that step 5 is obtained is molten
Liquid prepares polymer solids by precipitating, drying process.
In the preparation method of above-mentioned sun-proof film forming polymer, the initiator is peroxide type initiators or idol
Nitrogen class initiator.
In the preparation method of above-mentioned sun-proof film forming polymer, the initiator is the 0.1- of all raw material total amounts
1wt%；The ethyl alcohol is the 40-80wt% of all raw material gross weights；Surplus is monomer.
The beneficial effects of the present invention are:
Sun-proof film forming polymer provided by the invention can be used for ethyl alcohol body in sunscreen product there is water resistant to wash ability
System's formula, can be used for aqueous systems formula, the polymer can provide emulsifying capacity simultaneously in aqueous systems formula, emulsifiable and steady
Grease and oiliness active matter in fixed formula.
Specific embodiment
Illustrate the present invention With reference to embodiment: but it is understood that these specific embodiments are only intended to
Illustrate the present invention, rather than limiting the invention.Those skilled in the art completely can under the inspiration of the present invention, to this
The specific embodiment or technical characteristic of invention improve, but these technology technical solutions by improvement or replacement,
Still fall within protection scope of the present invention.
Embodiment 1:
48g methacrylic acid, 192g are added in the 1L four-hole boiling flask equipped with nitrogen device, agitating device and peristaltic pump
N tert butyl acrylamide, 48g methyl methacrylate, 9.6g lauryl acrylate, 22.4g vinyl silicone oil (viscosity
200mPas) and 200g ethyl alcohol, lead to nitrogen and stirring and dissolving, form monomer solution.
8g benzoyl peroxide is added in 200g ethyl alcohol, is dispersed with stirring uniformly, forms initiator solution.
It is added in five mouthfuls of flasks of 2L equipped with nitrogen device, reflux condensing tube, electric blender, thermometer and peristaltic pump
200g ethyl alcohol stirs after leading to nitrogen and is warming up to 80 DEG C, if it is desired, can suitably pressurize to reach required temperature.
After system temperature rises to 80 DEG C, partial monosomy solution and initiator solution is added, starts simultaneously after a period of time
Residual monomer solution and initiator solution is added, it is 3 hours that the time, which is added,.
It is added after completing and continuing heat preservation 1 hour and starts near room temperature.It is after temperature reaches room temperature that resulting polymers are molten
Liquid precipitate, crushing simultaneously obtain polymer powder after drying.
Embodiment 2-7:
Technique is formulated such as the following table 1 with embodiment 1:
Table 1: the formula table of embodiment 2-7
Remarks:
*: for the mass fraction for accounting for total monomer weight；
*: it indicates to account for the mass fraction of reaction solution total weight
Comparative example 1
1 process of comparative example is same as Example 1, and difference is to be added without acrylic monomers.
Comparative example 2
2 process of comparative example is same as Example 1, and difference is to be added without acrylamide derivative monomer.
Comparative example 3
3 process of comparative example is same as Example 1, and difference is to be added without (methyl) acrylic acid C1-C4 Arrcostab list
Body.
Comparative example 4
3 process of comparative example is same as Example 1, and difference is to be added without vinyl silicone oil.
Comparative example 5
3 process of comparative example is same as Example 1, and difference is to be added without lauryl acrylate.
Using test:
Polymer of the present invention is respectively used to ethanol system and aqueous systems sunscreen formulas, evaluate SPF and
Water resistant washes ability.The sunscreen formulas of ethanol system such as the following table 2, the sunscreen formulas of aqueous systems such as the following table 3:
2 ethanol system formula of table
| Ingredient | Dosage (wt%) |
| Ethyl alcohol | 70 |
| Film forming polymer | 4 |
| Octocrilene | 8 |
| Octyl methoxycinnamate | 7 |
| Benzophenone-3 | 5 |
| Avobenzone | 3 |
| Glycerol | 3 |
Formula process for preparation: film forming polymer being slowly sprinkled into after dissolving completely in ethyl alcohol, then be separately added into other ingredients,
After simplified version dissolution.
3 aqueous systems formula of table
It is formulated process for preparation: preparing A phase, B phase and C phase respectively, A is added in C phase after the completion of preparation, stirring is equal
Be added to after even by B, using homogenizer it is fully emulsified uniformly after.
SPF test before water impregnates: being smeared on hyaline membrane after being sampled using sampler, opposite in 20 DEG C and 50%
Spf value is tested using SPF analyzer after forming a film naturally in the dark surrounds of humidity, is averaged for each sample test 3 times
Value.
SPF is tested after water impregnates: it is smeared on hyaline membrane after being sampled using sampler, it is opposite in 20 DEG C and 50%
In the dark surrounds of humidity naturally film forming be placed on is impregnated 120 minutes in deionized water after naturally dry, using SPF divide
Analyzer tests spf value, is averaged for each sample test 3 times.
Each polymer performance such as the following table 4 described in the embodiment of the present invention and comparative example:
Table 4: each polymer performance described in embodiment and comparative example
Remarks: the project of no data indicates that the formula system compatibility is bad, and formula prepares failure, is unable to test.
It can be seen that the vinyl silicone oil and (methyl) acrylic acid C of single sealing end or bi-end-blocking by above-mentioned experiment12-C18
Arrcostab be for the stability and water-resistance of system it is vital, the two significantly affects water-resistance and stability, passes through
Above-mentioned five kinds of monomers are combined, and under the simulated environment of practical application, can significantly improve the protection effect of ultraviolet light.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of sun-proof film forming polymer, which is characterized in that obtained by following monomer by emulsion polymerization:
Account at least one carboxylic acid monomer of total monomer weight 15-25wt%；
Account for the acrylamide derivative of at least one structure shown in formula I of total monomer weight 30-60wt%:
R1With R2For hydrogen or C4-C12Alkyl, but R1With R2It is not simultaneously hydrogen；
Account for (methyl) acrylic acid C1-C4 Arrcostab of total monomer weight 15-30wt%；
Account for (methyl) acrylic acid C12-C18 Arrcostab of total monomer weight 3-10wt%；
Account for single sealing end of total monomer weight 5-10wt% or the vinyl silicone oil of bi-end-blocking.
2. sun-proof film forming polymer according to claim 1, which is characterized in that the carboxylic acid monomer be selected from acrylic acid,
One of methacrylic acid, itaconic acid, fumaric acid, crotonic acid, maleic acid are a variety of.
3. sun-proof film forming polymer according to claim 1, which is characterized in that acrylamide described in the Formulas I is derivative
Object is N tert butyl acrylamide, N- t-octyl acrylamide, N, N- dioctyl acrylamide, N, N- dodecyl acryloyl
One or more of amine.
4. sun-proof film forming polymer according to claim 1, which is characterized in that (methyl) the acrylic acid C1-C4Alkyl
Ester be (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
One or more of (methyl) tert-butyl acrylate, (methyl) propyl acrylate.
5. sun-proof film forming polymer according to claim 1, which is characterized in that the second of single sealing end or bi-end-blocking
Alkenyl silicone oil, viscosity is within 1000mPas.
6. sun-proof film forming polymer according to claim 1, which is characterized in that (methyl) the acrylic acid C12-C18Alkane
Base ester is lauryl acrylate, octadecyl methacrylate, tridecyl acrylate, methacrylic acid cetyl ester
In it is one or more.
7. a kind of preparation method of the sun-proof film forming polymer as described in claim 1-6 is any, which is characterized in that including as follows
Step:
Step 1: monomer and ethyl alcohol being added in first reactor, stirring is opened and is mixed, be configured to monomer solution；
Step 2: all or part of initiator being added in ethyl alcohol, initiator solution is configured to；
Step 3: ethyl alcohol being added in second reactor, leads to nitrogen, stirs and be warming up to 50-90 DEG C；
Step 4: after second reactor is warming up to required temperature, addition partial monosomy solution and part initiator solution, one section
Start while being added monomer solution and initiator solution after time, time for adding is 3-10 hours；
Step 5: after initiator and monomer solution are added dropwise to complete, continuing held for some time, be down to room temperature after heat preservation, obtain
Polymer solution.
8. the preparation method of sun-proof film forming polymer according to claim 7, which is characterized in that further include step 6: will walk
Rapid 5 obtained polymer solutions prepare polymer solids by precipitating, drying process.
9. the preparation method of sun-proof film forming polymer according to claim 7, which is characterized in that the initiator was
Oxide-based initiator or azo-initiator.
10. the preparation method of sun-proof film forming polymer according to claim 7, which is characterized in that the initiator is
The 0.1-1wt% of all raw material total amounts；The ethyl alcohol is the 40-80wt% of all raw material gross weights；Surplus is monomer.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5204090A (en) * | 1991-05-30 | 1993-04-20 | Bristol Myers Squibb | Waterproof high-SPF sunscreen compositions |
| GB2357697A (en) * | 1998-09-30 | 2001-07-04 | Avon Prod Inc | Compositions having a sunscreen for use in personal cleansing products |
| CN1371268A (en) * | 1999-08-26 | 2002-09-25 | 巴斯福股份公司 | Cosmetic and/or pharmaceutical preparations with polymers containing polysiloxanes and the uses thereof |
| US20060116489A1 (en) * | 2002-01-04 | 2006-06-01 | L'oreal | Composition containing a silicone copolymer and an AMPS-like polymer and/or organic powder |
| CN102186452A (en) * | 2008-10-17 | 2011-09-14 | 巴斯夫欧洲公司 | Sunscreen and personal care compositions comprising a random terpolymer |
| CN105451821A (en) * | 2012-12-21 | 2016-03-30 | 阿克佐诺贝尔化学国际公司 | Skin care formulations |
-
2019
- 2019-01-18 CN CN201910049768.0A patent/CN109694450B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5204090A (en) * | 1991-05-30 | 1993-04-20 | Bristol Myers Squibb | Waterproof high-SPF sunscreen compositions |
| GB2357697A (en) * | 1998-09-30 | 2001-07-04 | Avon Prod Inc | Compositions having a sunscreen for use in personal cleansing products |
| CN1371268A (en) * | 1999-08-26 | 2002-09-25 | 巴斯福股份公司 | Cosmetic and/or pharmaceutical preparations with polymers containing polysiloxanes and the uses thereof |
| US20060116489A1 (en) * | 2002-01-04 | 2006-06-01 | L'oreal | Composition containing a silicone copolymer and an AMPS-like polymer and/or organic powder |
| CN102186452A (en) * | 2008-10-17 | 2011-09-14 | 巴斯夫欧洲公司 | Sunscreen and personal care compositions comprising a random terpolymer |
| CN105451821A (en) * | 2012-12-21 | 2016-03-30 | 阿克佐诺贝尔化学国际公司 | Skin care formulations |
Non-Patent Citations (2)
| Title |
|---|
| 薛绘等: "不同抗水成膜剂在水包油防晒体系中的性能研究", 《日用化学品科学》 * |
| 黄文润: "烯烃基碳硅氧烷树枝状大分子单体及其应用", 《有机硅材料》 * |
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