CN111206456A - Aqueous non-silicon release agent, its preparation method and water-based non-silicon release paper - Google Patents
Aqueous non-silicon release agent, its preparation method and water-based non-silicon release paper Download PDFInfo
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- CN111206456A CN111206456A CN202010125933.9A CN202010125933A CN111206456A CN 111206456 A CN111206456 A CN 111206456A CN 202010125933 A CN202010125933 A CN 202010125933A CN 111206456 A CN111206456 A CN 111206456A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 68
- 239000010703 silicon Substances 0.000 title claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- IULGYNXPKZHCIA-UHFFFAOYSA-N octadecyl carbamate Chemical group CCCCCCCCCCCCCCCCCCOC(N)=O IULGYNXPKZHCIA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 11
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000010 aprotic solvent Substances 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 19
- ZJKIBABOSPFBNO-OWOJBTEDSA-N 3-Hydroxypropenoate Chemical compound O\C=C\C(O)=O ZJKIBABOSPFBNO-OWOJBTEDSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 12
- BXXLBMBLLVIOKO-UHFFFAOYSA-N octadecylcarbamic acid Chemical compound CCCCCCCCCCCCCCCCCCNC(O)=O BXXLBMBLLVIOKO-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UIUJIQZEACWQSV-UHFFFAOYSA-N succinic semialdehyde Chemical compound OC(=O)CCC=O UIUJIQZEACWQSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 239000006082 mold release agent Substances 0.000 abstract description 4
- 229920002545 silicone oil Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 polyethylene octadecyl carbamate Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
Abstract
The invention relates to the field of release materials, in particular to an aqueous non-silicon release agent, a preparation method thereof and aqueous non-silicon release paper. The water-based non-silicon release agent comprises a substrate layer and a release layer, wherein the release layer consists of the water-based non-silicon release agent and water. The chemical name of the water-based non-silicon mold release agent is octadecyl carbamate 3-hydroxy polyacrylate, and in the preparation method of the water-based non-silicon mold release agent, the main raw materials comprise: 3-aldehyde propionic acid, carbamic acid and n-octadecanol, and comprises seven reaction steps in total. The water-based non-silicon release paper can be widely applied to various fields, is more environment-friendly, and does not have the phenomenon of silicon transfer in the fields of application and electronic product production, particularly FPC production; the preparation method of the water-based non-silicon release agent has high utilization rate of raw materials, and the obtained product has high purity; the water-based non-silicon release agent can improve the release force of the release paper, so that the release paper can be better released.
Description
Technical Field
The invention relates to the field of release materials, in particular to an aqueous non-silicon release agent, a preparation method thereof and aqueous non-silicon release paper.
Background
The release paper is anti-sticking paper which can prevent the adhesion of the prepreg and protect the prepreg from being polluted, and is mainly used in the fields of silica gel production, FPC production and the like. At present, the types of release paper are various, and mainly include silicone oil release paper, silicone oil release film, wax-coated paper, special plastic release film and the like.
The preparation method mainly comprises two steps of coating silicone oil on one surface of the base paper and coating a plastic spraying film on the other surface of the base paper. The silicone oil is the release agent of the centrifugal paper, and the release paper is mainly used for production of self-adhesive labels, adhesive tapes, die cutting and the like. However, when the release paper is applied to the field of FPC production, a silicone oil transfer phenomenon exists, which affects the printability of FPC on one hand and the electrification of FPC on the other hand, and the release force of the silicone oil release agent is relatively light.
The silicone oil release film is obtained by coating silicone oil on a PET substrate, and is mainly used for adhesive sticker, label, adhesive tape production, die cutting processing and the like.
The wax-coated paper is obtained by coating a wax coating on base paper, the release agent is wax, and the release paper is mainly used in the fields of food and cooking and is not suitable for FPC production because the wax is easy to dissolve and fall off and has poor temperature resistance.
The special plastic release film adopts plastic release with low surface energy, so that the release paper has better effect when being used in the field of FPC production, can resist high temperature of reflow soldering and wave soldering, does not have the phenomenon of silicon transfer, but has high price, and the base material is mostly imported.
In view of the above circumstances, chinese patent application No. CN102691231A discloses a non-silicon release paper, which uses polyethylene octadecyl carbamate as a release agent, and thus the non-silicon release paper has a reasonable price, can well avoid the silicon transfer phenomenon, and is sought by FPC manufacturers. However, in recent years, as the environment protection concept is promoted by the country, the environment protection requirement of each manufacturing industry is more and more strict, and the release agent based on oil solubility cannot meet the requirement of the times, and is inherently to be further improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the water-based non-silicon release paper which can avoid the occurrence of silicon transfer phenomenon and is more environment-friendly.
The above object of the present invention is achieved by the following technical solutions: the utility model provides an aqueous non-silicon release paper, includes the substrate layer and leaves the type layer, it comprises aqueous non-silicon release agent and water to leave the type layer.
Through adopting above-mentioned technical scheme, waterborne non-silicon release agent mixes with water and forms from the type layer, and what obtain like this from the type layer than oil solubility leaves the type layer more environmental protection, reduces the use of solvents such as benzene, petrol, makes the product of direct and user contact such as sticker, sticky tape from type paper, and is more green healthy. In addition, the water-based non-silicon release agent does not contain silicone oil, so that the phenomenon of silicon transfer can be avoided when the release agent is applied to the field of FPC production.
The present invention in a preferred example may be further configured to: the water-based non-silicon release agent is octadecyl carbamate 3-hydroxy polyacrylate, and the release layer is obtained by coating a water solution of the water-based non-silicon release agent with the concentration of 3-15% on a substrate layer.
By adopting the technical scheme, the octadecyl carbamate 3-hydroxyl polyacrylate has certain water solubility due to the existence of free carboxyl, and the functional group providing the release force is mainly octadecyl carbamate. Experience shows that 3-15% of aqueous non-silicon release agent aqueous solution can provide better release force.
The present invention in a preferred example may be further configured to: the substrate layer includes that a raw paper layer and a PET plastics drench the rete, waterborne non-silicon is drenched rete, raw paper layer for leaving type layer, PET plastics from the top down in proper order from the type paper.
By adopting the technical scheme, the structure is the release paper with the single-sided release function.
The present invention in a preferred example may be further configured to: the substrate layer includes that a raw paper layer and two PET plastics drench the rete, waterborne non-silicon drenches rete, raw paper layer, PET plastics drench the rete, from the type layer for leaving type layer, PET plastics from the top down in proper order from the type paper.
Through adopting above-mentioned technical scheme, such a structure is that a two-sided detachable type is from type paper.
The second purpose of the invention is to provide a preparation method of the water-based non-silicon release agent, and the water-based non-silicon release agent obtained by the method has strong water solubility and is not easy to generate silicon transfer phenomenon.
The technical purpose of the method is realized by the following technical scheme: a preparation method of an aqueous non-silicon release agent is characterized in that the main raw materials for preparing the aqueous non-silicon release agent comprise: 3-formyl propionic acid, carbamic acid, n-octadecyl alcohol; the chemical name of the aqueous non-silicon release agent is as follows: octadecyl carbamate 3-hydroxy polyacrylate;
the preparation of the octadecyl carbamate 3-hydroxyl polyacrylate mainly comprises the following steps:
step 1, reacting n-octadecanol with carbamic acid under the catalysis of an aprotic solvent and sodium ethoxide at the reaction temperature of 70 ℃, acidifying, extracting and recrystallizing to obtain an octadecyl carbamic acid crystal;
step 2, mixing 3-aldehyde propionic acid and water according to a mass ratio of 1:1, adding an initiator, reacting for 10-15min at the temperature of 30 ℃ under the condition of 2atm, uniformly heating to 80 ℃ at a constant speed of 1 ℃/min, keeping constant temperature for reacting for 1h, adding 3-aldehyde propionic acid with the same mass as the initial amount of the 3-aldehyde propionic acid, continuing to react for 1h, and stopping heating to obtain poly-3-hydroxy acrylic acid, wherein n is more than 5000;
step 3, removing water and low molecules which do not participate in polymerization under the conditions of 90-110 ℃ and vacuum degree of-0.05 Mpa to-0.06 Mpa to obtain poly 3-hydroxyacrylic acid crystals with the purity of more than 99.7 percent;
step 4, dissolving the poly-3-hydroxy acrylic acid crystal in an aprotic solvent, adding phenol, and carrying out esterification reaction at 140 ℃ for 45min to obtain an aprotic solvent solution of poly-3-hydroxy phenyl acrylate;
step 5, dissolving the octadecyl carbamic acid crystal obtained in the step 1 in an aprotic solvent according to the mass ratio of 1:1, slowly dropwise adding the solution of the poly-3-phenyl hydroxyacrylate obtained in the step 4 in the aprotic solvent, using calcium oxide as a dehydrating agent, keeping the temperature of the reaction kettle at 170 ℃ in the whole dropwise adding process, stopping dropwise adding after 2h, and finishing the reaction after 30min to obtain a mixture A and residues;
step 6, filtering the mixture A obtained in the step 5 to remove residues, adding water, heating in a water bath at 60 ℃, shaking, and carrying out hydrolysis reaction for 30min to obtain a mixture B;
and 7, removing water, the aprotic solvent, phenol and other low molecules from the mixture at the temperature of 100-.
By adopting the technical scheme, in the step 1, a substitution reaction mainly occurs, under the action of sodium ethoxide, carboxyl and amino in carbamic acid lose protons to form Lewis acid, wherein N-ion has strong nucleophilic attack and performs SN2 substitution reaction with primary alcohol carbon in N-octadecanol to obtain octadecyl carbamic acid, and the subsequent operation mainly has the effect of purification;
in the step 2, the enol form of the 3-aldehyde propionic acid is 3-hydroxy acrylic acid, the polymerization reaction can obtain poly 3-hydroxy acrylic acid, the environment with double atmospheric pressure is to improve the saturated vapor pressure of each component, and is more favorable for the addition polymerization reaction, the reaction is carried out for 10-15min at 30 ℃, the aim of providing a mild chain initiation condition is to provide a mild chain initiation condition, then the temperature is uniformly increased to 80 ℃ according to the speed of 1 ℃/min, the aim of mild transition is carried out to the chain transfer process, the constant temperature reaction is kept for 1h, the process of maintaining the chain transfer rapid reaction is a process, 3-aldehyde propionic acid with the same mass as the initial amount of the 3-aldehyde propionic acid is added, the reaction is continued for 1h, the materials are supplemented for the polymerization reaction, so that the polymerization reaction is more sufficient;
in the step 3, the vacuum dehydration and low molecular removal are performed to ensure that the poly-3-hydroxyacrylic acid obtained by extraction achieves the maximum purity;
in the step 4, esterification reaction can be formed to obtain a product of poly 3-hydroxy phenyl acrylate, and the purpose of the step is to protect free carboxyl in poly 3-hydroxy acrylic acid and avoid excessive anhydride by-products formed by alcoholic hydroxyl and octadecyl carbamic acid in the next step;
in the step 5, the reaction process is controlled slowly, so that side reactions are mainly avoided, the esterification reaction in the step is more difficult to perform than the esterification reaction in the step 4, and calcium oxide is added as a dehydrating agent;
step 6, adding a certain amount of water and heating, wherein the carboxyl protected in the step 4 is mainly reduced to be in an original state, and at the moment, as the phenolic ester is easier to hydrolyze than the alcohol ester, the solid hydrolysis selectivity is stronger, and the hydrolysis of an active group providing a release force cannot be caused;
and 7, purifying by adopting a vacuum dehydration and low molecular removal mode, and obtaining the octadecyl carbamate 3-hydroxyl polyacrylate product with higher purity to the greatest extent.
The present invention in a preferred example may be further configured to: in the substitution reaction in the step 1, the mass parts of the substances are as follows:
270 parts of n-octadecanol;
60 parts of carbamic acid;
400 parts of an aprotic solvent;
15 parts of sodium ethoxide;
in the esterification reaction in the step 4, the mass parts of the substances are as follows:
60 parts of poly (3-hydroxyacrylic acid) crystals;
200 parts of an aprotic solvent;
95 parts of phenol;
in the esterification reaction in the step 5, the mass parts of the substances are as follows:
314 parts of octadecyl carbamic acid crystal;
355 parts of an aprotic solvent solution of poly-3-phenyl hydroxyacrylate;
140 parts of calcium oxide.
In the hydrolysis reaction in the step 6, the mass parts of the substances are as follows:
670 parts of a mixture A;
and 30 parts of water.
By adopting the technical scheme, when the components with the mass ratio are applied in the synthesis step, the final product can be better obtained, the yield is high, and the raw materials are not wasted.
The present invention in a preferred example may be further configured to: the aprotic solvent may be one of butyl ether, cyclohexane, and n-octane.
By adopting the technical scheme, the butyl ether, the cyclohexane and the n-octane have high boiling points and small polarity, and are preferred aprotic solvents.
The third purpose of the present invention is to provide an aqueous non-silicon release agent, which is prepared according to the method of the foregoing steps 1 to 7, and which can improve a good release force for release paper, so that the release paper can be released better.
In summary, the invention includes at least one of the following beneficial technical effects:
firstly, the water-based non-silicon release paper can be widely applied to various fields, is more environment-friendly, and does not have the phenomenon of silicon transfer in the fields of application and electronic product production, particularly FPC production;
secondly, the preparation method of the water-based non-silicon release agent has high utilization rate of raw materials, and the obtained product has high purity;
and thirdly, the water-based non-silicon release agent can improve the better release force for the release paper, so that the release paper is better released.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
The water-based non-silicon release paper comprises a substrate layer and a release layer, wherein the release layer consists of a water-based non-silicon release agent and water. The water-based non-silicon mold release agent is octadecyl carbamate 3-hydroxy polyacrylate, and the mold release layer is obtained by coating a water solution of the water-based non-silicon mold release agent with the concentration of 3-15% on a substrate layer. The base material layer comprises a raw paper layer and a PET plastic laminating film layer, and the water-based non-silicon release paper comprises a release layer, the PET plastic laminating film layer and the raw paper layer from top to bottom in sequence.
The main raw materials for preparing the water-based non-silicon release agent comprise: 3-formyl propionic acid, carbamic acid, n-octadecyl alcohol; the chemical name of the aqueous non-silicon release agent is as follows: octadecyl carbamate 3-hydroxy polyacrylate;
the preparation of octadecyl carbamate 3-hydroxypolyacrylate of this example mainly comprises the following steps:
step 1, reacting n-octadecanol with carbamic acid under the catalysis of an aprotic solvent and sodium ethoxide at the reaction temperature of 70 ℃, acidifying, extracting and recrystallizing to obtain an octadecyl carbamic acid crystal;
step 2, mixing 3-aldehyde propionic acid and water according to a mass ratio of 1:1, adding an ammonium persulfate initiator, reacting for 10min at the temperature of 30 ℃ under the condition of 2atm, uniformly heating to 80 ℃ at a constant speed of 1 ℃/min, keeping constant temperature for reaction for 1h, adding 3-aldehyde propionic acid with the same mass as the initial amount of the 3-aldehyde propionic acid, continuing to react for 1h, and stopping heating to obtain poly-3-hydroxy acrylic acid, wherein n is more than 5000;
step 3, removing water and low molecules which do not participate in polymerization under the conditions of 90 ℃ and vacuum degree of-0.05 Mpa to obtain poly 3-hydroxy acrylic acid crystals with the purity of more than 99.7 percent;
step 4, dissolving the poly-3-hydroxy acrylic acid crystal in an aprotic solvent, adding phenol, and carrying out esterification reaction at 140 ℃ for 45min to obtain an aprotic solvent solution of poly-3-hydroxy phenyl acrylate;
step 5, dissolving the octadecyl carbamic acid crystal obtained in the step 1 in an aprotic solvent according to the mass ratio of 1:1, slowly dropwise adding the solution of the poly-3-phenyl hydroxyacrylate obtained in the step 4 in the aprotic solvent, using calcium oxide as a dehydrating agent, keeping the temperature of the reaction kettle at 170 ℃ in the whole dropwise adding process, stopping dropwise adding after 2h, and finishing the reaction after 30min to obtain a mixture A and residues;
step 6, filtering the mixture A obtained in the step 5 to remove residues, adding water, heating in a water bath at 60 ℃, shaking, and carrying out hydrolysis reaction for 30min to obtain a mixture B;
and 7, removing water, aprotic solvent, phenol and other low molecules from the mixture at the temperature of 100 ℃ and the vacuum degree of-0.05 Mpa to obtain the octadecyl carbamate 2-hydroxy polyacrylate crystal with the purity of more than 99.1 percent.
In the substitution reaction in the step 1, the mass parts of the substances are as follows:
270 parts of n-octadecanol;
60 parts of carbamic acid;
400 parts of an aprotic solvent;
15 parts of sodium ethoxide;
in the esterification reaction in the step 4, the mass parts of the substances are as follows:
60 parts of poly (3-hydroxyacrylic acid) crystals;
200 parts of an aprotic solvent;
95 parts of phenol;
in the esterification reaction in the step 5, the mass parts of the substances are as follows:
314 parts of octadecyl carbamic acid crystal;
355 parts of an aprotic solvent solution of poly-3-phenyl hydroxyacrylate;
140 parts of calcium oxide;
in the hydrolysis reaction in the step 6, the mass parts of the substances are as follows:
670 parts of a mixture A;
and 30 parts of water.
The aprotic solvent may be one of butyl ether, cyclohexane, and n-octane.
Example 2
The present embodiment is similar to the shape and structure of embodiment 1, except that the substrate layer is slightly different, and two release layers are provided. The non-silicon type release paper of waterborne of this embodiment, the substrate layer includes that a raw paper layer and two PET plastics drench the rete, and non-silicon type release paper from the top down drenches rete, raw paper layer, PET plastics and drenches the rete, from the type layer for from type layer, PET plastics in proper order.
Example 3
The shape and structure of the present example are substantially the same as those of example 1, and the only difference is that the process parameters in step 2, step 3 and step 7 are slightly different in the method for preparing the aqueous non-silicon release paper. In the step 2, 3-aldehyde propionic acid is mixed with water and then added with an initiator, and the reaction time is changed to 15min under the conditions of 2atm and 30 ℃; in the step 3, the temperature of the dehydration is changed to 110 ℃, and the vacuum degree of the dehydration is changed to-0.06 Mpa; in step 7, the temperature of the dehydration is changed to 120 ℃, and the vacuum degree of the dehydration is changed to-0.06 Mpa.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples, and for example, octadecyl carbamate 3-hydroxypolyacrylate, which is not obtained by the method provided in the present specification, is used as a release agent, and the technical teaching obtained from the description of the present invention is included in the scope of the present invention as long as the performance satisfies the requirements, and the technical scheme within the spirit of the present invention is included in the scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. The utility model provides a waterborne is non-silicon from type paper, includes the substrate layer and leaves the type layer, its characterized in that: the release layer is composed of an aqueous non-silicon release agent and water.
2. The aqueous non-silicon release paper according to claim 1, characterized in that: the water-based non-silicon release agent is octadecyl carbamate 3-hydroxy polyacrylate, and the release layer is obtained by coating a water solution of the water-based non-silicon release agent with the concentration of 3-15% on a substrate layer.
3. The aqueous non-silicon release paper according to claim 1, characterized in that: the substrate layer includes that a raw paper layer and a PET plastics drench the rete, waterborne non-silicon is drenched rete, raw paper layer for leaving type layer, PET plastics from the top down in proper order from the type paper.
4. The aqueous non-silicon release paper according to claim 1, characterized in that: the substrate layer includes that a raw paper layer and two PET plastics drench the rete, waterborne non-silicon drenches rete, raw paper layer, PET plastics drench the rete, from the type layer for leaving type layer, PET plastics from the top down in proper order from the type paper.
5. The preparation method of the water-based non-silicon release agent is characterized in that the main raw materials for preparing the water-based non-silicon release agent comprise: 3-formyl propionic acid, carbamic acid, n-octadecyl alcohol; the chemical name of the aqueous non-silicon release agent is as follows: octadecyl carbamate 3-hydroxy polyacrylate;
the preparation of the octadecyl carbamate 3-hydroxyl polyacrylate mainly comprises the following steps:
step 1, reacting n-octadecanol with carbamic acid under the catalysis of an aprotic solvent and sodium ethoxide at the reaction temperature of 70 ℃, acidifying, extracting and recrystallizing to obtain an octadecyl carbamic acid crystal;
step 2, mixing 3-aldehyde propionic acid and water according to a mass ratio of 1:1, adding an initiator, reacting for 10-15min at the temperature of 30 ℃ under the condition of 2atm, uniformly heating to 80 ℃ at a constant speed of 1 ℃/min, keeping constant temperature for reacting for 1h, adding 3-aldehyde propionic acid with the same mass as the initial amount of the 3-aldehyde propionic acid, continuing to react for 1h, and stopping heating to obtain poly-3-hydroxy acrylic acid, wherein n is more than 5000;
step 3, removing water and low molecules which do not participate in polymerization under the conditions of 90-110 ℃ and vacuum degree of-0.05 Mpa to-0.06 Mpa to obtain poly 3-hydroxyacrylic acid crystals with the purity of more than 99.7 percent;
step 4, dissolving the poly-3-hydroxy acrylic acid crystal in an aprotic solvent, adding phenol, and carrying out esterification reaction at 140 ℃ for 45min to obtain an aprotic solvent solution of poly-3-hydroxy phenyl acrylate;
step 5, dissolving the octadecyl carbamic acid crystal obtained in the step 1 in an aprotic solvent according to the mass ratio of 1:1, slowly dropwise adding the solution of the poly-3-phenyl hydroxyacrylate obtained in the step 4 in the aprotic solvent, using calcium oxide as a dehydrating agent, keeping the temperature of the reaction kettle at 170 ℃ in the whole dropwise adding process, stopping dropwise adding after 2h, and finishing the reaction after 30min to obtain a mixture A and residues;
step 6, filtering the mixture A obtained in the step 5 to remove residues, adding water, heating in a water bath at 60 ℃, shaking, and carrying out hydrolysis reaction for 30min to obtain a mixture B;
and 7, removing water, the aprotic solvent, phenol and other low molecules from the mixture at the temperature of 100-.
6. The preparation method of the aqueous non-silicon release agent according to claim 5, characterized in that in the substitution reaction of step 1, the mass parts of the substances are as follows:
270 parts of n-octadecanol;
60 parts of carbamic acid;
400 parts of an aprotic solvent;
15 parts of sodium ethoxide;
in the esterification reaction in the step 4, the mass parts of the substances are as follows:
60 parts of poly (3-hydroxyacrylic acid) crystals;
200 parts of an aprotic solvent;
95 parts of phenol;
in the esterification reaction in the step 5, the mass parts of the substances are as follows:
314 parts of octadecyl carbamic acid crystal;
355 parts of an aprotic solvent solution of poly-3-phenyl hydroxyacrylate;
140 parts of calcium oxide;
in the hydrolysis reaction in the step 6, the mass parts of the substances are as follows:
670 parts of a mixture A;
and 30 parts of water.
7. The method for preparing the aqueous non-silicon release agent according to the claims 5 and 6, characterized in that: the aprotic solvent may be one of butyl ether, cyclohexane, and n-octane.
8. An aqueous non-silicon release agent, characterized in that: prepared according to the process of claims 5-7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732240A (en) * | 2002-12-31 | 2006-02-08 | 3M创新有限公司 | Release compositions and articles made therefrom |
| CN101696557A (en) * | 2009-10-15 | 2010-04-21 | 广州市白云区春源纸业制品厂 | Release paper for artificial leather, preparation method and application thereof |
| CN102691231A (en) * | 2012-05-10 | 2012-09-26 | 广州市鸿鹄胶粘材料科技有限公司 | Non-silicon release paper |
| CN102816484A (en) * | 2012-08-23 | 2012-12-12 | 浙江池河科技有限公司 | Release agent, its preparation method and release paper prepared from the same |
| CN110016263A (en) * | 2019-04-22 | 2019-07-16 | 广州山木新材料科技有限公司 | A kind of aqueous mould release and preparation method thereof and construction method |
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2020
- 2020-02-27 CN CN202010125933.9A patent/CN111206456B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732240A (en) * | 2002-12-31 | 2006-02-08 | 3M创新有限公司 | Release compositions and articles made therefrom |
| CN101696557A (en) * | 2009-10-15 | 2010-04-21 | 广州市白云区春源纸业制品厂 | Release paper for artificial leather, preparation method and application thereof |
| CN102691231A (en) * | 2012-05-10 | 2012-09-26 | 广州市鸿鹄胶粘材料科技有限公司 | Non-silicon release paper |
| CN102816484A (en) * | 2012-08-23 | 2012-12-12 | 浙江池河科技有限公司 | Release agent, its preparation method and release paper prepared from the same |
| CN110016263A (en) * | 2019-04-22 | 2019-07-16 | 广州山木新材料科技有限公司 | A kind of aqueous mould release and preparation method thereof and construction method |
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