阅读说明：本技术 一种酪素改性方法 (A kind of casein method of modifying ) 是由 黄清根 王正青 李扬勇 黄玮 黄惠昌 于 2019-09-23 设计创作，主要内容包括：本发明公开了一种酪素改性方法,包括以下步骤：a.引发剂溶液的制备；b.单体溶液的制备；c.酪素溶液的制备；d.酪素的改性。通过本发明提供的改性方法制备得到的改性酪素成膜后既透水透气,还保证了湿擦后的固色效果,且薄膜具有良好的柔韧性,改善了酪素自身成膜硬脆的问题,扩大了酪素在涂料、油墨等领域的应用,利用改性酪素制备一种凹版水墨冲淡剂具有广泛的相容性和优异的印刷适性。(The invention discloses a kind of casein method of modifying, comprising the following steps: the preparation of a. initiator solution；B. the preparation of monomer solution；C. the preparation of casein solution；D. the modification of casein.Both water-permeable and air permeable after modified Casein that the method for modifying provided through the invention is prepared film forming, colour fixation after also assuring wet rubbing, and film has good flexibility, improve the hard crisp problem of casein itself film forming, casein is expanded in the application in the fields such as coating, ink, preparing a kind of gravure ink diluent using modified Casein has extensive compatibility and excellent printability.)

1. a kind of casein method of modifying, which comprises the following steps:

Persulfate: being configured to the solution of 0.05~0.15wt% by a. preparation of initiator solution, and solvent is deionized water, is stirred It mixes uniformly, for use；

2~5g cyclosiloxane: being configured to the solution of 3~5wt% by the b. preparation of monomer solution, and solvent is deionized water, is added dropwise PH adjusting agent adjusts pH and is greater than 8, stirs evenly, obtain monomer solution A, for use；3~6g amide compound is configured to 3~ The solution of 5wt%, solvent are deionized water, are stirred evenly, and obtain monomer B solution, for use；

25~30g casein: being configured to the solution of 12~18wt% by the c. preparation of casein solution, and solvent is deionized water, drop Add pH adjusting agent, adjusts pH and be greater than 8, be heated to 70~80 DEG C, keep the temperature, for use；

D. the modification of casein: 10~20ml of initiator solution is measured, is divided into uniform two parts, first by a initiator solution and list Body solution A is added dropwise in the casein solution of heat preservation simultaneously, after stirring 0.5~1h, then another initiator solution and monomer B is molten Liquid instills simultaneously, after continuing 1~2h of stirring, is concentrated under the conditions of 80~90 DEG C, it is cooling to get.

2. casein method of modifying as described in claim 1, which is characterized in that the persulfate is selected from ammonium persulfate, over cure One of sour sodium, potassium peroxydisulfate or a variety of mixing.

3. casein method of modifying as described in claim 1, which is characterized in that the cyclosiloxane is selected from cyclotetrasiloxane, ring One of five siloxanes, six siloxanes of ring or a variety of mixing.

4. casein method of modifying as described in claim 1, which is characterized in that the cyclosiloxane is selected from tetramethyl tetravinyl One of cyclotetrasiloxane, five vinyl cyclopentasiloxane of pentamethyl, six ethylene basic ring of hexamethyl, six siloxanes are a variety of Mixing.

5. casein method of modifying as described in claim 1, which is characterized in that the amide compound is selected from methylol acryloyl One of amine, Diacetone Acrylamide, acrylamide or a variety of mixing.

6. casein method of modifying as described in claim 1, which is characterized in that the cyclosiloxane, amide compound, casein Mass ratio be 1:(1~2): (6~8).

7. casein method of modifying as described in claim 1, which is characterized in that the drop of a initiator solution in the step d It is 5~20min between added-time.

8. a kind of modified Casein, which is characterized in that it is by casein method of modifying system as described in any one of claims 1 to 7 For what is obtained.

9. a kind of application of modified Casein as claimed in claim 8, which is characterized in that it is applied to printing ink or leather applies Adorn agent field.

10. a kind of ink diluent, which is characterized in that it prepares raw material and includes at least: modified Casein as claimed in claim 8 18~22wt%, 8~12wt% of ethylene glycol, 35~45wt% of hydroxymethyl cellulose, surplus are deionized water.

Technical field

The present invention relates to paint field more particularly to a kind of casein method of modifying.

Background technique

Casein is a kind of widely used water-soluble film forming agent, is in the nature a kind of compound egg by extracting in milk White matter, Environmental Safety meet at present on the market to the demand of environmentally friendly machine.Past casein is used for always leather finish, edge Yu Qiyu leather bonds power is strong, and it is good to be formed by film temperature tolerance, it is even more important that casein film has excellent ventilative Aqueous, this is not available for many coating.

Nowadays the application range of casein is gradually expanded to printing ink paint field, but there is also some problems in application, by Contain a large amount of polar groups, such as amino, hydroxyl, carboxyl in casein, forms stronger interaction between these groups, make The film that must be formed is discontinuous, although this can assign casein film breathable permeable performance, also result in film it is hard it is crisp, prolong Stretching property is small, easy fracture defect, simultaneously as hydrophily is too strong, film there is also not humidity, intolerant to wet rubbing the problem of.

Summary of the invention

To solve the above-mentioned problems, the first aspect of the present invention provides a kind of casein method of modifying, comprising the following steps:

Persulfate: being configured to the solution of 0.05~0.15wt% by a. preparation of initiator solution, and solvent is deionization Water stirs evenly, for use；

2~5g cyclosiloxane: being configured to the solution of 3~5wt% by the b. preparation of monomer solution, and solvent is deionized water, PH adjusting agent is added dropwise, adjusts pH and is greater than 8, stir evenly, obtain monomer solution A, for use；3~6g amide compound is configured to 3 The solution of~5wt%, solvent are deionized water, are stirred evenly, and obtain monomer B solution, for use；

25~30g casein: being configured to the solution of 12~18wt% by the c. preparation of casein solution, and solvent is deionization PH adjusting agent is added dropwise in water, adjusts pH and is greater than 8, be heated to 70~80 DEG C, keeps the temperature, for use；

D. the modification of casein: 10~20ml of initiator solution is measured, is divided into uniform two parts, first by a initiator solution It is added dropwise in the casein solution of heat preservation simultaneously with monomer solution A, after stirring 0.5~1h, then by another initiator solution and list Body B solution instills simultaneously, after continuing 1~2h of stirring, is concentrated under the conditions of 80~90 DEG C, it is cooling to get.

As a kind of perferred technical scheme, the persulfate is in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate One or more mixing.

As a kind of perferred technical scheme, the cyclosiloxane is selected from cyclotetrasiloxane, cyclopentasiloxane, six silicon oxygen of ring One of alkane or a variety of mixing.

As a kind of perferred technical scheme, the cyclosiloxane is selected from t etram-ethyltetravinylcyclotetrasiloxane, five first One of five vinyl cyclopentasiloxane of base, six ethylene basic ring of hexamethyl, six siloxanes or a variety of mixing.

As a kind of perferred technical scheme, the amide compound is selected from hydroxymethyl acrylamide, diacetone acrylamide acyl One of amine, acrylamide or a variety of mixing.

As a kind of perferred technical scheme, the cyclosiloxane, amide compound, casein mass ratio be 1:(1~ 2): (6~8).

As a kind of perferred technical scheme, the time for adding of a initiator solution is 5~20min in the step d.

The second aspect of the present invention provides a kind of modified Casein, is prepared by casein method of modifying as described above It arrives.

The third aspect of the present invention provides a kind of application of modified Casein as described above, be applied to printing ink or Leather finishing agent field.

The fourth aspect of the present invention provides a kind of ink diluent, prepares raw material and includes at least: changing as described above Property casein 18~22wt%, 8~12wt% of ethylene glycol, 35~45wt% of hydroxymethyl cellulose, surplus be deionized water.

The utility model has the advantages that both water-permeable and air permeable after the modified Casein film forming that the method for modifying provided through the invention is prepared, Colour fixation after also assuring wet rubbing, and film has good flexibility, improves the hard crisp problem of casein itself film forming, Casein is expanded in the application in the fields such as coating, ink, using modified Casein prepare a kind of gravure ink diluent have it is extensive Compatibility and excellent printability.

Specific embodiment

In conjunction with preferred implementation method of the invention below detailed description and including embodiment can be further understood that this hair Bright content.Unless otherwise indicated, all technologies used herein and scientific term all have general with the application fields Logical technical staff's is generally understood identical meaning.If mentioned in the definition and the application of the concrete term disclosed in the prior art Any definition supplied is inconsistent, then term provided herein of being subject to defines.

It is used in the present context, unless being clearly dictated in context, otherwise without the spy of the single plural form of restriction Sign is also intended to the feature including plural form.It will also be appreciated that term as used herein " by ... preparation " it is synonymous with "comprising", " comprising ", " including ", " having ", "comprising" and/or " including " indicate stated group when used in this manual Object, step, method, product or device are closed, but does not preclude the presence or addition of one or more of the other composition, step, method, system Product or device.In addition, using " preferred ", " preferably ", " preferred " etc. to be when describing presently filed embodiment Refer to, can provide the embodiment of the present invention of certain beneficial effects in some cases.However, under identical circumstances or other feelings Under condition, other embodiments are also likely to be preferred.In addition to this, not dark to the statement of one or more preferred embodiments Show that other embodiments are unavailable, is also not intended to exclude other embodiments except the scope of the present invention.

To solve the above-mentioned problems, the first aspect of the present invention provides a kind of casein method of modifying, comprising the following steps:

Persulfate: being configured to the solution of 0.05~0.15wt% by a. preparation of initiator solution, and solvent is deionization Water stirs evenly, for use；

2~5g cyclosiloxane: being configured to the solution of 3~5wt% by the b. preparation of monomer solution, and solvent is deionized water, PH adjusting agent is added dropwise, adjusts pH and is greater than 8, stir evenly, obtain monomer solution A, for use；3~6g amide compound is configured to 3 The solution of~5wt%, solvent are deionized water, are stirred evenly, and obtain monomer B solution, for use；

25~30g casein: being configured to the solution of 12~18wt% by the c. preparation of casein solution, and solvent is deionization PH adjusting agent is added dropwise in water, adjusts pH and is greater than 8, be heated to 70~80 DEG C, keeps the temperature, for use；

D. the modification of casein: 10~20ml of initiator solution is measured, is divided into uniform two parts, first by a initiator solution It is added dropwise in the casein solution of heat preservation simultaneously with monomer solution A, after stirring 0.5~1h, then by another initiator solution and list Body B solution instills simultaneously, after continuing 1~2h of stirring, is concentrated under the conditions of 80~90 DEG C, it is cooling to get.

a.The preparation of initiator solution: persulfate is configured to the solution of 0.05~0.15wt%, solvent is deionization Water stirs evenly, for use.

Initiator, also known as radical initiator, generate free radicals vulnerable to thermal decomposition, and free radical can be by unsaturated carbon Carbon key is opened, initiated polymerization.Persulfate initiator in aqueous solution it is ionizable go out two have free electron sulfuric acid Radical ion, activity is high, the polymerization reaction occurred suitable for lotion or aqueous solution.

In some preferred embodiments, the persulfate is in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate One or more mixing；It is further preferred that the persulfate is potassium peroxydisulfate (No. CAS: 7727-21-1).

b.The preparation of monomer solution: 2~5g cyclosiloxane is configured to the solution of 3~5wt%, solvent is deionized water, PH adjusting agent is added dropwise, adjusts pH and is greater than 8, stir evenly, obtain monomer solution A, for use；3~6g amide compound is configured to 3 The solution of~5wt%, solvent are deionized water, are stirred evenly, and obtain monomer B solution, for use.

Casein is native protein, and solution has certain film forming, is used for the neck such as printing ink paint, leather finishing agent Domain, but due to self structure, casein is hard crisp in the presence of film forming, and intolerant to wet friction, extensibility is small, and easy fracture easily mildews Problem, it is therefore desirable to be grafted other monomers on its main chain and improve.

In some preferred embodiments, the cyclosiloxane is selected from cyclotetrasiloxane, cyclopentasiloxane, six silicon oxygen of ring One of alkane or a variety of mixing；It is further preferred that the cyclosiloxane be selected from t etram-ethyltetravinylcyclotetrasiloxane, One of five vinyl cyclopentasiloxane of pentamethyl, six ethylene basic ring of hexamethyl, six siloxanes or a variety of mixing；More into one Step, the cyclosiloxane is selected from t etram-ethyltetravinylcyclotetrasiloxane (No. CAS: 2554-06-5), five vinyl of pentamethyl One in cyclopentasiloxane (No. CAS: 17704-22-2), six ethylene basic ring of hexamethyl, six siloxanes (No. CAS: 18304-82-0) Kind.

In some preferred embodiments, the amide compound is selected from hydroxymethyl acrylamide, diacetone acrylamide acyl One of amine, acrylamide or a variety of mixing；It is further preferred that the amide compound be hydroxymethyl acrylamide and The mixing of Diacetone Acrylamide.

In some preferred embodiments, the hydroxymethyl acrylamide (No. CAS: 924-42-5) and diacetone acrylamide The mass ratio of amide (No. CAS: 2873-97-4) is 1:3.

Inventor has found that film forming possessed by casein is on its molecule to contain great amount of hydroxy group, carboxyl, ammonia under study for action Base isopolarity group, so can spontaneous crosslinking film forming, but also just because of the presence of these groups, extremely strong hydrophily causes Film forming poor water resistance, intolerant to wet friction.Inventor cooperates amides by continuous exploration discovery, using cyclosiloxane monomer Casein film water resistance after monomer is grafted jointly is substantially improved, also not easy to break under wet friction, which is because, cyclosiloxane has There is excellent hydrophobic performance, the hydrophily of a part of casein can be shielded, and ring structure is to provide physics in cross-linking system Node, the branch formed after cooperation amide compound grafting, significantly improves the flexibility of film forming.Inventor also unexpectedly sends out Existing, the extensibility of film forming has been similarly obtained improvement, thus it is speculated that this is because multiple casein molecules can be grafted on cyclosiloxane, by casein Biomolecule partition is opened, and the interaction between polar group is reduced, and reduces the entanglement of molecule interchain, and then solution is more when covering with paint, lacquer, colour wash, etc. Easily expansion.

c.The preparation of casein solution: 25~30g casein is configured to the solution of 12~18wt%, solvent is deionization PH adjusting agent is added dropwise in water, adjusts pH and is greater than 8, be heated to 70~80 DEG C, keeps the temperature, for use.

Although containing a large amount of hydrophilic radical on casein, dissolubility is poor, and the interaction between polar group makes It obtains it to be only swollen in neutral aqueous solution, can just be dissolved in alkaline solution or concentrated acid solution.

In some preferred embodiments, the cyclosiloxane, amide compound, casein mass ratio be 1:(1~ 2): (6~8)；It is further preferred that the mass ratio of the cyclosiloxane, amide compound, casein is 1:1:7.

Inventor is by carefully studying discovery, when cyclosiloxane, amide compound, casein carry out instead in certain proportion Water-fast, flexible, water-permeable and air permeable should can be obtained and the good film forming of colour fixation, which is because, hydroxymethyl acrylamide is due to nitrogen Methylol activity on atom is stronger, can make with a variety of reaction-ity group reactions, the crosslinkable groups that it is provided when film forming Film forms a tridimensional network, while the other components of film coated surface can be moved to anchor ingot, avoids it arbitrary Migration and migration, with the increase of hydroxymethyl acrylamide dosage, the number of crosslinking points is also gradually increased on polymer segment, at The crosslink density of film increases after film, and the cross-linked network of generation is gradually intensive, and solvent resistance improves, therefore fixing property is also It enhances, however the degree of cross linking increase to form a film can cause permeable breathable to be deteriorated；The homopolymer of Diacetone Acrylamide or copolymerization Object is not soluble in water, but has " aquatic respiration ", this is because double methyl on its molecule neither generate crosslinking, also has one Fixed steric hindrance separates the strand of entanglement, thus can for gas molecule, hydrone by providing channel, and itself and casein After hydrophilic radical condensation on main chain, the partial hydrophilicity of casein itself is not only shielded, further improve that casein easily mildews asks Topic；Cyclosiloxane then provides firm crosslinking for casein film forming, further improves the properties of casein film forming.

D. the modification of casein: 10~20ml of initiator solution is measured, is divided into uniform two parts, first by a initiator solution It is added dropwise in the casein solution of heat preservation simultaneously with monomer solution A, after stirring 0.5~1h, then by another initiator solution and list Body B solution instills simultaneously, after continuing 1~2h of stirring, is concentrated under the conditions of 80~90 DEG C, it is cooling to get.

Casein and grafted monomers generate crosslinking under initiator effect, and selection, dosage and the dropwise addition mode of initiator are to junket The raising of disposition energy plays an important role.

In some preferred embodiments, the time for adding of a initiator solution is 5~20min in the step d； It is further preferred that the time for adding of a initiator solution is 15min in the step d.

Inventor pass through a large amount of exploration discoveries, in a certain order to casein carry out grafting and to the addition of initiator into The modified Casein of properties equilibrium can be prepared, which is because, cyclosiloxane is first grafted on casein point in row regulation On son, the active site on casein molecule is more, contributes to form uniform cross-linked network, and in the effect of cyclosiloxane Under, more active groups are unfolded and exposed to casein molecule, and when subsequent use amide monomer is grafted, grafting rate is mentioned Height, modified effect are significantly increased；It since the activity of grafted monomers is strong, can not only be reacted with casein, it is also possible to occur certainly Body condensation, therefore must be very accurate to the regulation that initiator is added, it just can guarantee effective progress of graft reaction, speed be added Too fast or too slow all modified effect to be caused poor, casein filming performance does not increase anti-drop.

In some preferred embodiments, the casein method of modifying the following steps are included:

Persulfate: being configured to the solution of 0.12wt% by a. preparation of initiator solution, and solvent is deionized water, stirring Uniformly, for use；

4g cyclosiloxane: being configured to the solution of 4wt% by the b. preparation of monomer solution, and solvent is deionized water, and pH is added dropwise Regulator adjusts pH and is greater than 8, stirs evenly, obtain monomer solution A, for use；4g amide compound is configured to the molten of 4wt% Liquid, solvent are deionized water, are stirred evenly, and obtain monomer B solution, for use；

28g casein: being configured to the solution of 16wt% by the c. preparation of casein solution, and solvent is deionized water, and pH is added dropwise Regulator adjusts pH and is greater than 8, be heated to 75 DEG C, keeps the temperature, for use；

D. the modification of casein: initiator solution 18ml is measured, is divided into uniform two parts, first by a initiator solution and list Body solution A is added dropwise in the casein solution of heat preservation simultaneously, after stirring 0.5h, then by another initiator solution and monomer B solution Instill simultaneously, continue after stirring 1.5h, be concentrated under the conditions of 85 DEG C, it is cooling to get.

The second aspect of the present invention provides a kind of modified Casein, is prepared by casein method of modifying as described above It arrives.

The third aspect of the present invention provides a kind of application of modified Casein as described above, be applied to printing ink or Leather finishing agent field.

The fourth aspect of the present invention provides a kind of ink diluent, prepares raw material and includes at least: changing as described above Property casein 18~22wt%, 8~12wt% of ethylene glycol, 35~45wt% of hydroxymethyl cellulose, surplus be deionized water.

In some preferred embodiments, the raw material for preparing of the ink diluent includes at least: changing as described above Property casein 20wt%, ethylene glycol 10wt%, hydroxymethyl cellulose 40wt%, surplus be deionized water.

In some preferred embodiments, the hydroxymethyl cellulose is that the hydroxymethyl cellulose of 3~5wt% is pre-dispersed Solution；It is further preferred that the hydroxymethyl cellulose is the pre-dispersed solution of hydroxymethyl cellulose of 4wt%.

Diluent will not generally change the adhesiveness, printability and other rheological properties of ink, and diluent is added can be with The depth tone of ink colors is deployed, being such as added when adjusting printing plate color separation deviation is agent of losing lustre, and allows to improve in print speed printing speed In the case where on a small quantity be added be toner, Chen Moli addition can increase gloss and firmness, particularly with ink supply cycle performance Diluent is the object of indispensability for poor low-speed printer.

The preparation method of ink diluent described herein can for it is well known to those skilled in the art any one, such as The following steps are included: modified Casein, ethylene glycol, hydroxymethyl cellulose are add to deionized water, high-speed stirred is uniformly mixed, To obtain the final product.