WO2007134499A1

WO2007134499A1 - Graft copolymer, process of preparation and use thereof, colorant release agent and articles thereof

Info

Publication number: WO2007134499A1
Application number: PCT/CN2006/003486
Authority: WO
Inventors: Powen Chung
Original assignee: Shanghai Difang Textile Technological Flocking Co., Ltd.; Shanghai Newtech Fabric Printing Co., Ltd.
Priority date: 2006-05-16
Filing date: 2006-12-19
Publication date: 2007-11-29
Also published as: CN100344830C; CN1844573A

Abstract

A copolymer obtainable by poly[acrylic acid (acrylate)-styrene] grafted on starch,the process of preparation and use thereof are provided. The poly[acrylic acid (acrylate)-styrene] is (meth)acrylic -(meth)acrylate- styrene terpolymer.The graft copolymer has a molecular weight in the range of 2500-30000 Dalton and is of the formula : Wherein AGU represents a structure unit of starch, n represents the recurring number of the structure unit, and poly[acrylic acid (acrylate)-styrene] represents poly[acrylic acid(acrylic ester)-styrene]. A cold-pressing transfer printing paper is also provided.The coating of the above graft copolymer is applied on the surface of the transfer printing paper.

Description

Graft copolymer, preparation method and use thereof, pigment release agent and preparation thereof

This invention relates to the technical field of pigment release agents used in the transfer printing process in the textile printing and dyeing industry. In particular, the present invention relates to a novel poly[acrylic acid (styrene)-starch graft copolymer paste used in a pigment release agent for cold transfer printing paper (ie, a dye release agent) and preparation thereof The method and use also relate to a pigment release agent comprising the above graft copolymer and an article having a coating formed from the pigment release agent, such as a cold transfer printing paper. The cold transfer printing paper with the separation layer prepared by the pigment spacer coating coating according to the present invention can be applied to natural fiber fabrics such as cellulose fibers, wool, cotton, silk, etc., and can also be used for polyester, nylon, Acrylic fiber and other synthetic fabrics. Background technique

Transfer printing (hereinafter sometimes referred to as "transfer") has become a new method of industrial decoration and textile printing. The method comprises the following steps: printing a suitable dye ink on a special paper by printing to print a pattern or text to be printed, and printing the dyed side of the transfer paper with the printed fabric. The film is transferred to the fabric by pressure and wetting to dissolve the dye oil from the paper.

At present, the transfer printing method can be classified into a dry transfer method, that is, a thermal transfer type and a pressure sensitive transfer type, and a wet transfer method, that is, a cold transfer peeling method and a solvent transfer peeling type. The earliest transfer printing process was a sublimation hot melt transfer printing as one of the thermal transfer methods. According to the British "Dyeing Association Association" in 1971 and Japan's "Processing Technology" 1972 "Transfer Printing" album introduction, the general sublimation method hot melt transfer printing, the transfer of transfer printing paper to the fabric of the dye can not be all Absorption, there is always a part of the dye remaining on the surface of the fabric and the paper base, which is the main color yield of the transfer printing process, and the color fastness of the printed fabric is poor. the reason. At the temperature of 200 ° C or lower, only 39 dyes can be used for the transfer printing paper, and nearly 20% - 30% of the dye remains on the paper base after the transfer printing. Therefore, in the years to come, the biggest concern for transfer printing is how to minimize the residual dye on the paper base, which is conducive to cost savings and helps to solve the environmental pollution of dye residues. The wet cold transfer printing process. Sublimation hot melt transfer printing process can only process chemical fiber fabrics, especially polyester fiber fabrics, while cellulose fibers and natural fibers such as wool, silk and cotton must be processed by wet cold transfer printing. In the wet cold transfer printing process, in order to allow the dye to be sufficiently transferred from the transfer printing paper, a transfer layer or a release layer is first applied to the paper base (see Japanese Patent No. 22094). Especially after the 1970s, there have been a variety of transfer or release layers for transfer printing inks, but they all have their limitations: 1. The transfer rate of the ink, the printed color is transmitted through or through the release layer. The thin film is in contact with the paper base and the amount of peeling is insufficient. 2. The peeling film is excessively hydrophobic. Due to the wet transfer of the water-based dye, the excessive hydrophobicity of the peeling film causes the substrate to be inconsistent with the surface tension of the paper. The integrity and clarity of the printed pattern; 3. Back-sticking and blocking, the ink does not stick and re-stick after a short period of film formation, but when the film is unloaded after printing, it is found that the back side of the paper is stuck to the front side, resulting in Serious problem of wetness in the surface; 4. Low pH resistance, when the printed paper is overprinted with the wetted fabric, the paper peeling layer is not resistant to strong alkali, causing serious penetration of the pattern after transfer printing. The type is fuzzy, the pattern is unclear; 5. The adhesion fastness is poor, and the dye pattern to be printed is poor in adhesion, and it can be discolored by hand rubbing, and the pollution is serious. These limitations limit the practical application value of various types of transfer printing inks that appeared after the 1970s. At the same time, due to the above reasons, it cannot be completely embodied or applied to the cold transfer printing process and then transferred to various fibers. Summary of the invention

The present invention is directed to the limitations of the transfer layer or the release layer of the conventional transfer printing ink. A new poly(acrylic acid ester-styrene)-starch graft copolymer and a pigment release agent for cold transfer printing paper containing the graft copolymer, having a separation layer made by using the pigment release agent The cold transfer printing paper used in the cold transfer printing process can isolate the penetration of the ink into the paper and improve the ink transfer rate; has the proper hydrophobicity and hydrophilic printability, ensures the complete printing of the substrate, and makes the printed pattern complete and clear; Produces the problem of wet inside the surface; has a good pH adaptation range; the dye pattern is well adhered, and no color fading occurs. The invention promotes the further development of the printing and dyeing industry towards the environmentally friendly economy.

One aspect of the present invention is to provide a novel poly[acrylic acid]-styrene]-starch graft copolymer.

A second aspect of the present invention provides a process for producing the above poly(acrylic acid)-starch graft copolymer.

The three aspects of the present invention are the use of the above-described graft copolymer which can be used to prepare a novel pigment release agent for cold transfer printing paper. The cold transfer printing paper with the separation layer prepared by coating with the pigment isolating agent can be applied to natural fiber fabrics such as cellulose fibers, wool, cotton, silk, etc., and can also be used for synthetic fibers such as polyester, nylon, acrylic and the like. On the fabric, a clear, brightly printed product is produced.

According to a fourth aspect of the invention, there is provided a dye separating agent comprising the above graft copolymer.

A fifth aspect of the invention relates to an article having a coating formed of the above-described pigment release agent, such as a cold transfer printing paper. DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an infrared spectrum of a poly [acrylic acid-butyl acrylate-styrene]-starch ternary graft copolymer prepared in Example 1.

2 is a nuclear magnetic resonance spectrum of the pigment release agent emulsion prepared in Example 3. detailed description

In the following, various aspects of the invention are described in detail.

First, the poly[acrylic acid]-styrene graft copolymer of the present invention and a process for producing the same are described.

In the present invention, the term "poly(acrylic acid)-starch graft copolymer" means a material obtained by graft copolymerization of poly[acrylic acid]-styrene and starch. Among them, poly [acrylic acid]-styrene is a terpolymer of acrylic acid, (meth) acrylate or styrene, or a binary copolymer of (meth) acrylate or styrene. "(Meth)acrylic acid" in the present invention means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or methacrylate, and styrene includes substituted and unsubstituted styrene. In the present invention, a graft copolymer of a terpolymer of acrylic acid, acrylate or styrene and starch is preferred.

In the present invention, the acrylate and methacrylate respectively include an alkyl ester of acrylic acid and methacrylic acid, preferably a C1-C10 mercapto ester, more preferably a propyl group and a butyl ester.

The poly[acrylic acid (styrene)-styrene graft copolymer of the present invention has a weight average molecular weight of from 2,500 to 30,000 Daltons, and the structural formula of the graft copolymer is expressed as:

Wherein AGU represents a structural unit constituting starch, n represents a repeating number of the structural unit, and Poly [Acryl ic acid (Acryiate)-Styrene] represents poly[propionate-styrene]. According to Zhang Tiantian's 1992, "Transformed Starch" and Long Jianying, Long Xiangyun, and Ye Guoxun's paper "Quantum Chemistry Research on the Electronic Structure of Starch Molecules (I): Characteristics of Structural Units, Glycosidic Bonds and Hydrogen Bonds , (Guangxi Science. Vol. 9, No. 1, 2002, pp. 34-37-42), etc. It is generally believed that the reactive center of starch molecules is C3. The hydroxyl group at the C2 and C6 positions, the active sequence is the hydroxyl group at the C3 position > the hydroxyl group at the C2 position > the hydroxyl group at the C6 position, which is initiated by most people using a peroxide, a guanamine nitrate or a redox system initiator to initiate free radical living polymerization. The reaction mechanism infers that poly[acrylic acid]-styrene is mainly grafted at the C3 position of the starch molecule.

The poly[acrylic acid (styrene)-styrene graft copolymer of the present invention is prepared by an emulsion polymerization method. Specifically, the following two steps are included: controlling monomer concentration, initiator concentration, emulsifier concentration, polymerization temperature to form poly[acrylic acid]-styrene; oxidizing starch by an initiator to produce starch Under the condition of free radicals, poly[acrylic acid (styrene)-styrene] is graft-copolymerized with starch to form a poly[acrylic acid (styrene)-styrene]-graft copolymer. The grafting rate is over 25 %, and the product is hydrophilic at this time.

In the present invention, the raw material monomers acrylic acid, (meth) acrylate and styrene are industrial first-grade products, which are commercially available directly from the market.

When preparing the polyacrylic acid-(meth)acrylate-styrene terpolymer, the concentration of the monomer is controlled such that the ratio of (meth)acrylic acid, (meth) acrylate, and styrene is approximately 1: 10: 2. 5. When the above poly((meth)acrylate-styrene] binary copolymer was prepared, the monomer concentration was controlled so that the ratio of (meth) acrylate to styrene was about 4:1.

Specifically, if 100 parts of the ternary graft copolymer is to be prepared, the control range of the mass of the monomer component added is: 35 to 40 parts of (meth) acrylate, 4 to 6 parts of (meth) acrylate, benzene 10 to 20 parts of ethylene. To prepare 100 parts of the binary graft copolymer, the control range of the mass of the monomer component is: 35 to 50 parts for (meth) acrylate and 10 to 20 parts for phenylethyl group.

5%。 The preferred concentration is 0.35%. The emulsifiers used in the polymerization system can be: higher fatty alcohol sulfates, such as sodium lauryl sulfate, sodium cetyl sulfate, sodium octadecanoate (this material is an anionic emulsifier and an acrylic emulsion phase). Melt, etc. And sorbitan monooleate, laurate, monostearate, etc., the purity is industrial grade first or more. In the usual conditions not for special paper bases and fabrics, sodium decanoate and sorbitan monooleate and monostearate are preferred as complex emulsifiers.

In the present invention, a preferred octadecyl sulfate and sorbitan monooleate, mono-hard acid and triethanolamine are used as a composite emulsifier, if 100 parts of a graft copolymer, an emulsifier, is to be prepared. The dosage range is controlled by: sorbitan monooleate ~ 0.25 parts, sodium octadecanoate ~ 0.1 parts, triethanolamine ~ 0.2 parts

In the present invention, the concentration of the initiator in the system is usually 0.05% to 0.2%, preferably 0.15%. The initiator may use a strong oxidizing agent such as a persulfate clock, ammonium persulfate, benzoyl peroxide, hydrogen peroxide or the like; or an ionic initiator such as azobisisobutyronitrile, azobisisovaleral or the like;铈 salt; or redox system initiator, such as persulfate clock-sodium bisulfite, ammonium persulfate-sodium bisulfite, potassium persulfate-ferrous sulfate, potassium persulfate-sodium thiosulfate, etc., purity Industrial first-class products and chemically pure, analytically pure. For poly[(meth)acrylic acid-(meth)acrylate-styrene]-starch graft copolymerization, potassium persulfate or sodium persulfate-sodium bisulfite is preferred as the initiator for the polymerization reaction; (Meth) acrylate-styrene]-starch graft copolymerization, azobisisobutyronitrile is preferred as the initiator of the polymerization reaction. In the grafting, when the amount of the polymerized molecules reaches 30,000 or more, the hydrophilicity is good.

In the present invention, a preferred persulfate clock-sodium bisulfite initiator is taken as an example. For 100 parts by mass of the graft copolymer, the amount of the initiator is controlled in the range of: sodium hydrogen sulfite to 0.1 part, potassium persulfate to 0.05. Share.

The starch used in the present invention is a modified starch having a degree of etherification of 0.7-1.2, usually an etherified starch obtained by using propylene oxide as an etherifying agent and epichlorohydrin as a crosslinking agent, which can be directly purchased from the market or It is prepared by one of ordinary skill in the art using conventional means.

In the present invention, the amount of the starch is from 18 to 25 parts, preferably 25 parts, per 100 parts by mass of the starch graft copolymer. The grafting rate is above 25% to ensure hydrophilicity. In the present invention, a monomer mixture composed of (meth)acrylic acid, (meth) acrylate and styrene, or composed of (meth) acrylate and styrene is added to an emulsion system composed of an emulsifier and an initiator. , we (for (meth)acrylic acid, (meth) acrylate and styrene ternary systems) or 60 ° C (for (meth) acrylate and styrene binary systems) initiated polymerization. The temperature of the system is automatically increased. When the temperature of the system reaches 85 °C, the modified starch with a degree of etherification of 0.7 to 1.2 is added, and the temperature is controlled at 70 to 85 °C, and the reaction is continued for 1 to 2 hours. When the system reaches a certain viscosity requirement, that is, the temperature is stopped to stop the reaction, and a poly[acrylic acid (styrene)-styrene]-graft copolymer is obtained, and the graft ratio is 25% or more.

For the determination of the product of the poly(acrylic acid)-starch graft copolymer, in order to eliminate the physical mixing, the emulsion sample after the completion of the above reaction is added with a certain amount of absolute ethanol to cause precipitation, and filtration is performed. After the precipitated product was added to a 0.5 mol / L NaOH solution, the ungrafted starch was separated by stirring at 50 ° C for 1 hour, and the filtered precipitated product was packed in a paper bag and placed in a Soxhlet extractor to extract with toluene. The agent was reflux-extracted for 24 hours to remove the homopolymer of styrene and acrylic acid and acrylate. Finally, the product in the paper bag was dried and solidified to obtain a pure graft product. Infrared photodetection of the solidified grafted product was carried out to observe the absorption peaks of non-starch molecules such as the characteristic absorption peak of the carbonyl (C-0) of 1726 cnf ¹ on the spectrum, and it was confirmed that poly [acrylic acid] was formed. Styrene]-starch graft copolymer.

The poly[acrylic acid (styrene)-styrene graft copolymer obtained by the above process is dispersed in the emulsion, and in the case of direct use of the emulsion, it is required to be measured by a rotational viscometer at 25 °C. The content of the homopolymer is 0.3%, and the homopolymer content is 0. 3 %.

The graft copolymer emulsion thus obtained can be used as it is, or can be isolated, dried and purified by means known in the art.

Next, the use of the graft copolymer of the present invention in transfer printing will be described. The graft copolymer thus obtained can be used for preparing the pigment release agent for cold transfer printing paper of the present invention, which comprises the above-mentioned graft copolymer of poly[acrylic acid]-styrene and starch, sulfated oil. , phosphate esters and silica or palygorskite as fillers. The pigment release agent for cold transfer printing paper can be applied to various printing machines such as flexographic printing machines, gravure printing machines, screen printing machines, and the like, and printing transfer printing papers for various fabrics.

The pigment release agent for cold transfer printing paper prepared according to the present invention contains, by mass percentage: poly [acrylic acid (styrene)-styrene]-starch graft copolymer 35% - 85 %; silica as a filler 0.05% -0.5% or palygorskite 3 % - 9 %; sulphated oil as additive auxiliaries 0.2% - 1.8 %, defoamer 0.1 % - 0.8 %, wetting agent 0.5% -2%, The balance is water.

In the present invention, a small amount of a solid substance is added as a filler, and a smaller amount of a liquid substance is added as an auxiliary agent for improving certain properties of the system and being convenient for application.

In the present invention, the filler materials are mainly ultrafine powder grade silica (such as vapor phase silica, nano silica) or silicate or palygorskite, depending on the targeted fabric. Choose to use.

In the present invention, the sulfated oily substance includes, for example, castor oil sulfate, sodium stearyl sulfate, etc., and sodium oleoate is usually used.

In the present invention, the antifoaming agent includes a phosphate such as tributyl phosphate and an alcohol such as n-octanol. Tributyl phthalate is preferred under the usual conditions not for special paper bases and fabrics.

In the present invention, a wetting agent, carboxypyrrolidone or the like, may be optionally added depending on the intended fabric.

The fillers and auxiliaries of the present invention are commercially available, and the purity is industrial. CP grade or AR grade.

The method of preparing the above-described pigment release agent for cold transfer printing paper is as follows. In the poly[acrylic acid (styrene)-starch graft copolymer prepared by the present invention, an auxiliary agent and a filler are added to obtain a pigment release agent for cold transfer printing paper of the present invention. Specifically, The above-mentioned dye release agent is obtained by adding a sulfated oil, a phosphate ester, and silica or palygorite as a filler to the graft copolymer.

The pigment release agent produced as described above is excellent in compatibility with the dye component, has good latex stability, and has high film formation and light stability. However, it should be noted that in the process of copolymerization of poly(acrylic acid)-starch graft copolymer system, if the degree of grafting is too high, the coating film will become hard and cold transfer The printing paper insulation layer has an adverse effect, so the concentration of the acrylic monomer is controlled to be < 6%, the polymerization molecular weight of the styrene-acrylic acid is more than 30,000, and the grafting ratio is more than 25%. The pigment spacer has good chemical stability and mechanical stability, and has excellent printability. And its rheological properties are ideal for all types of coating equipment. It guarantees good operation even under the most demanding parts, provides excellent wet rub resistance, and avoids malfunctions such as misprints and paper breaks during paper printing.

Taking the preferred scheme as a model, the preparation process of the pigment release agent for cold transfer printing paper is specifically described as follows: triethanolamine, sodium lauryl sulfate (sodium lauryl sulfate) and water are used as an emulsion, and sulfurous acid is added under stirring. Sodium hydrogen hydride and potassium persulfate, heated to 50 ° C as an initiator, mixed with (meth)acrylic acid, (meth) acrylate (such as butyl acrylate, ethyl methacrylate) and styrene monomer The addition of the initiating emulsifier initiates polymerization. The temperature of the system is automatically increased. When the temperature reaches 85 ° C, the modified starch with a degree of etherification of 0.7 to 1.2 is added. The temperature is controlled at 70 85 ° C, and the reaction is continued for 1 h to 2 h to achieve acrylic acid. - Graft copolymerization of styrene copolymer with starch, the graft ratio is about 28%. Further, an ultrafine powder grade silica or silicate or palygorskite, castor oil sodium sulfate, and tributyl phosphate is added to the above copolymer emulsion, and if necessary, a wetting agent, carboxypyrrolidone, is added, and the water is adjusted to 100%. That is, a pigment spacer for cold transfer printing paper is obtained. The pigment release agent for the cold transfer printing paper is a milky white liquid having a viscosity of 300 to 1600 Pa·s, and the Charon Cup No. 2 cup has a flow rate of 20 to 70 seconds at 25 °C.

The pigment release agent for cold transfer printing paper according to the present invention can be applied to natural fiber fabrics such as cellulose fibers, wool, cotton, silk, or cold transfer printing paper for synthetic fiber fabrics such as polyester, nylon, acrylic, and inkjet transfer. Cold transfer printing paper and cold transfer printing Art. The original cold transfer printing paper caused the dye and paper fibers to be fixed due to the imbalance and incompleteness of the hydrophilicity and hydrophobicity of the release agent, so that the residual color of the transferred paper was nearly 50%, even after 86 years. Foreign manufacturers who study wet transfer also have low transfer rate due to incompleteness of the release agent and incompletely shielding the pigment, and the residual amount of paper-based dyes is too large, which wastes raw materials and seriously pollutes the environment. Since the main component of the pigment release agent used in the cold transfer printing paper of the present invention is a polymer graft copolymer coated on a paper base of transfer printing paper, a film-like medium can be formed, and a temporary shielding can be produced. When the dye is printed on the printing tool, it does not have a strong affinity with the paper base of the transfer printing paper, and can promote the transfer of the dye ink to the fabric. In particular, the pigment release agent of the present invention has an excellent effect on inkjet transfer printing. Since digital inkjet printing, the entire image is composed of fine color dots, a higher jet dot density is required. This is the resolution of the usual title. Different base fabrics have different resolution requirements. The yarn count, density and fabric texture of the fabric all affect the resolution. Therefore, in the world, inkjet printing requires a layer of contact on the surface of the fabric to color the dots, and then through steaming, water washing, and finally finishing the printing process. Even the production capacity of the Netherlands ST0YK company is only 4. 6m7h. This process limits the development of digital inkjet. After the cold transfer coating of the present invention is applied, the ink jet is discharged, and the yield can be greatly improved. The transfer coating of the present invention is capable of accepting color points of dpi 360 - 720 and ultra fine 720 dpi X 720 dpi color points. The image fineness on textiles reaches the Dutch ST0YK reactive dye inkjet printing standard.

The above-mentioned pigment release agent for cold transfer printing paper can be applied to various printing machines such as flexographic printing machines, gravure printing machines, screen printing machines, and the like, and printing transfer papers for various types of fabrics. Specifically, fine, colorful, and layered transfer printing paper can be printed by a rotary screen printing machine, a flat screen printing machine, a gravure printing machine, a flexographic printing machine, a flatbed offset printing machine, and an inkjet printer.

Flexographic printing is a method of printing ink through an anilox roller using a flexible resin plate, which has a embossing property, and is a flexible rubber surface in terms of its printing characteristics. In contact with printing paper, it has offset characteristics. From the transfer paper material, it uses water-based ink and can be printed by the cell, which has gravure characteristics. Flexo printing is a light pressure printing process with a printing line pressure of about lkgf / cm. At the same time, the thickness of the ink layer of flexographic printing is about 5~10% _Q iM. The printing plate image of the gravure printing is lower than the surface of the printing plate, and the hierarchical density of the graphic is represented by the depth and density of the concave mesh. The gravure is direct printing, and the ink in the concave portion of the printing plate is directly transferred to the substrate to form an image portion. When printing, the ink is coated on the printing plate, and then the ink in the blank surface of the printing plate is scraped off with a doctor blade to fill the concave portion. The ink in the lower part is kept down and transferred to the surface of the substrate by printing pressure to complete the printing. The gravure printed line pressure is ll ~ 18kgf/cm. However, since the inking of the gravure is that the printing plate directly contacts the ink in the ink tank, there is no ink transfer system, and the paper coating material is required to be strict. The rotary screen printing process is a printing method between the gravure roll printing and the flat screen printing in terms of its printing characteristics.

The article according to the invention has a coating formed from the pigment release agent of the invention. The article may, for example, be a cold transfer printing paper having a coating formed on the surface of the paper base by the pigment release agent of the present invention. The "paper base" herein may be any paper base commonly used in the art, such as writing paper, offset paper, printing paper, glossy paper, wrapping paper, printing paper, and the like. The dye release agent of the present invention is applied onto a paper base by a known coating means such as doctor blade coating, web coating, extrusion coating, roll coating or the like to form a cold transfer printing paper. Such cold transfer printing paper not only has the function of shielding carrier, but also has good printing adaptability and transferability, and at the same time, it has anti-seepage, heavy-duty resistance, rapid transfer pattern to fabric and adapting to roll during transfer. The paper is formed into the necessary moisture resistance and tear resistance. The transfer printing paper coated with the release agent of the invention also solves the problem that the amount of dye residue on the paper is too large when the transfer printing paper is transferred, so that the transfer rate is over 90%, which not only saves the dyeing material, but also Reduced environmental pollution. Therefore, the present invention promotes the further development of the printing and dyeing industry toward the environmentally friendly economy.

The examples are provided below to more specifically describe the invention, but the invention is not limited by these examples. In the examples, "parts" means "parts by weight" unless otherwise specified. In the following examples, the measurement of the viscosity was carried out in accordance with the national standard GB/T1723-93 "Coating viscosity measurement method" using a Zahn cup coated cup.

Example 1

Preparation of poly [acrylic acid-butyl acrylate-styrene]-starch ternary graft copolymer

The sulphuric acid is added in an amount of 0. 1 part of sulphuric acid. The sulphuric acid is added to the sulphuric acid. Sodium hydrogenate and 0.05 parts potassium persulfate, heated to 50. C as initiator; 40 parts of butyl acrylate, 4 parts of acrylic acid and 10 parts of styrene were added dropwise to the initiator emulsion. After the polymerization was initiated, the system was automatically heated to 85 ° C, ie, the degree of etherification was added. 7 - 1. 2 modified starch (hydroxyl shielded) 25 parts, control temperature is 70 ~ 85 ° C, continue to react lh-2h, grafting rate is about 32%, to achieve acrylic (styrene) - styrene The graft copolymerization of the copolymer and the starch gives a poly[acrylic acid]-styrene graft copolymer emulsion for preparing a pigment spacer, wherein the graft copolymer has a weight average molecular weight of about 19,000 Daer. pause. The infrared ray spectrum of the cured product of the emulsion was measured under the following conditions, and the obtained infrared spectrum is shown in Fig. 1.

Instrument: NICOLET NEXUS 470;

Method: multiple attenuation total reflection TR);

Resolution: 4cm- ¹ ; Scan: 64 SCANS

It can be seen from Fig. 1 that 1103 cm-\1020 cm- ¹ is the infrared absorption peak of starch molecules, 756 cm ^_1 and 696 cm- ¹ are caused by the upper CH vibration absorption on the stupid ring, and 1726 cm- ¹ is the carbonyl group (C). The characteristic absorption peak of =0), 1726 cm" ¹ , 1444 cm - 1155 cnf ¹ indicates that there are structural units of acrylate in the polymer molecule. From the above analysis, it is seen that the acrylic acid (meth) and styrene copolymer are grafted on the starch molecule. Poly[acrylic acid (styrene)-starch graft copolymer is formed. When acrylate and styrene are grafted with starch, the polymerization molecular weight of acrylate and styrene is more than 30,000, and the ternary copolymerization thereof The grafting rate is around 30%. Example 2

1份的十二烷之间。 The poly [(meth) acrylate-styrene] - starch binary graft copolymer was prepared in the experimental reactor, first 0.25 parts of triethanolamine, 5.8 parts of water and 0.1 parts of dodecane Sodium sulphate was injected into an emulsion, and 0.1 parts of azobisisobutyronitrile (AIBN) was added under stirring, and the temperature was raised to 60 ° C as an initiator; 40 parts of methyl methacrylate and styrene 10 were added. The monomer mixed droplets are added to the initiator emulsion, and after the polymerization is initiated, the system is automatically heated to 90 Torr, that is, the modified starch (hydroxyl shielded) having a degree of etherification of 0.7 to 1.2 is added, and the temperature is controlled. Under the condition of 75 ~ 85 °C, the reaction was continued for lh-2h to realize the graft copolymerization of methacrylate-styrene copolymer and ^: powder. The weight average molecular weight is about 15,000 Daltons. The molecular weight of the polymerization is 30,000 or more, the graft ratio is about 32%, and the hydrophilicity is good.

Example 3

Preparation of pigment spacer

3份的蓖麻油硫酸0. 0. 3 parts of castor oil sodium sulfate 0. 3 parts of eucalyptus oil sodium sulfate 0. 3份和三丁的三丁酯。 3 parts, palygorskite (palygorskite) 1 amount of water, after stirring the above substances, then added tributyl phosphate 0.3 parts and! 1⁄2 pyridine ketone 0. 2 parts, and finally adjusted to 100 parts (100%) with water, which is a pigment release agent for cold transfer printing paper (hereinafter referred to as "PE - 2 3⁄4").

The pigment spacer for the cold transfer printing paper is a blue-light milky white liquid with a solid content of about 48% and a viscosity of 800 to 900 Pa·s. The flow rate of the 2nd cup of the Zahn Cup is 25 - 40 seconds at 25 °C. .

The pigment spacer emulsion was subjected to nuclear magnetic resonance (NMR) experiments using the following apparatus and method, and the NMR actual map is shown in Fig. 2.

Instrument: Bruker DMX500 NMR;

Method: Heavy water D ₂ 0 system emulsion, MIL

It can be seen from Fig. 2 that the chemical shift δ is 1. 5 ~ 2. 5ppm of the proton peak is mainly A signal peak of methylene and methine on the acrylic-butyl acrylate-styrene copolymer backbone grafted onto the powder. The proton peak with a δ of 3.3 to 4.01 ppm is mainly produced by hydrogen atoms on the carbon of the ester group in the starch molecule, CI, C4, C5, C6 and butyl acrylate. A peak having a δ of about 4.7 ppm is caused by hydrogen in residual water molecules in the emulsion. The peak of δ of 5.0 ~ 6.2 ppm is the signal peak of the shield peak in the hydroxyl group attached to C6 in the starch molecule and the residual initiator emulsifier in other systems. δ is

The peak of 9.55ppm is the proton peak of the aldehyde group formed at the C2 position after the ring-opening bond between the C2 and C3 under the action of the graft copolymerization counterinitiator, and C3 becomes the grafting site. From the above analysis, it was found that the acrylic acid-butyl acrylate-styrene copolymer was grafted on the C3 of the starch molecule to form a poly[acrylic acid-butyl acrylate-styrene]-starch graft copolymer. The graft ratio is about 32%.

Example 4

Cotton fabrics for pigment transfer agents for cold transfer printing paper

Formulated by mass percentage:

Poly [acrylic acid - styrene] - starch graft copolymer ~ 72. / ₀ , gas phase grade osmolality is 0.3%,

Castor oil sodium sulfate is 0.7%

Tributyl phosphate is 0.2%

Adjust water to 100%.

In the industrial reactor, 2.5kg of triethanolamine, 58kg of water and lkg sorbitan monooleate are firstly injected into an emulsion, and lkg sodium hydrogen sulfite and 0.5kg potassium persulfate are added under stirring to raise the temperature to 50. °C as initiator; 400kg of butyl acrylate, 40kg of acrylic acid and 100kg of styrene were added dropwise to the initiator emulsion. After the polymerization was initiated, the system was automatically heated to 85 °C, ie, the degree of etherification was 0.7-1.2. Modified starch (hydroxyl shielded) 180kg, controlled temperature at 70~85 °C, continue to react for lh-2h, achieve graft copolymerization of acrylic acid-styrene copolymer and starch, weight average molecular weight is about 19000 Daltons. The molecular weight of the polymerization reaches 35,000 or more. Copolymerization here Grade silica added to the emulsion vapor 3kg, sodium castor oil ² kg, after stirring uniformly the foregoing, tributyl phosphate added 4kg, and finally water was adjusted to 1000kg (100%), cold transfer printing paper that is cotton Type pigment spacer. The pigment spacer for the cotton type cold transfer printing paper is a milky white liquid with a viscosity of ~900pa's, and the flow rate of the 2nd cup of the Chaen Cup is about 40 seconds at 25 °C.

Example 5

Synthetic cellulose fiber using pigment release agent for cold transfer printing paper

Formulated by mass percentage:

Poly [acrylic acid-styrene]-starch graft copolymer ~85%, silica 0.5%,

Castor oil sodium reduction is 10%

Tributyl phosphate is 0.1%,

The water is 4.4%.

The viscosity is 900 ~ 1200pa · s, and the flow rate of the 2nd cup of the Zahn Cup is 25 seconds at 25 °C.

In an industrial reactor, 2.5 kg of diethylaminoethanol, 58 kg of water and lkg of sodium cetyl sulfate (sodium cetyl sulfate) are firstly injected into an emulsion, and lkg sodium thiosulfate and lkg are added under stirring. 0.5kg persulfate clock, heating to 50 °C as initiator; 400 kg of butyl acrylate, 60 kg of acrylic acid and 180 kg of styrene were added dropwise to the initiator emulsion, and after the polymerization was initiated, the system was automatically heated to 85 ° C. , that is, the degree of etherification is 0.7

-1.2 modified starch (hydroxyl shielded) 210kg, controlled temperature at 70~85 °C, continue to react for lh-2h, achieve graft copolymerization of acrylic acid (styrene)-styrene copolymer and starch, weight average molecular weight It is about 22,000 Daltons. . Add 5kg of vapor phase grade silica and 100kg of castor oil sodium sulfate to the copolymer emulsion. After stirring the substance, add l-butyl phosphate lkg, and finally adjust the water to 1000kg (100%), which is cold transfer printing. Paper type pigment spacer for paper. The pigment release agent for the cotton type cold transfer printing paper is a milky white liquid with a viscosity of 900 ~ 1200 Pa · s, and the Chaen Cup 2 at 25 ° C The flow rate of the cup is about 70 seconds. The graft ratio is about 28%.

Example 6

Silk fabrics for cold transfer printing paper

Formulated by mass percentage:

Poly [acrylic acid (styrene)-styrene]-starch graft copolymer ~ 82 %, palygorskite 6%,

Castor oil bowl sodium is 5 %

Tributyl phosphate is 0.2%,

The water is 6.8%.

The viscosity is 500~700pa · s, and the flow rate of the fourth coated cup is 30 seconds at 25 °C. In the industrial reactor, 2.5kg of triethanolamine, 58kg of water and 0.9KG of sodium hexadecyl sulfate are injected into the emulsion, and lkg sodium hydrogen sulfite and 0.5kg potassium persulfate are added under stirring to raise the temperature to 50. °C as initiator; 400kg of butyl acrylate, 40kg of acrylic acid and 180kg of styrene were added dropwise to the initiator emulsion. After the polymerization was initiated, the system was automatically heated to 85 °C, ie, the degree of etherification was 0.7 - 1.2. Modified starch (hydroxyl shielded) 200kg, controlled temperature at 70~85 °C, continue to react for lh-2h, to achieve graft copolymerization of acrylic acid-stupyl ethylene copolymer with starch, weight average molecular weight is about 18,000 Daltons. The polymerization molecular weight of acrylate and styrene is about 32,000. Add 6% palygorskite and 50 kg of castor oil sodium sulfate to the copolymer emulsion. After stirring the above materials, add 2 kg of tributyl glutamate. Finally, adjust the water to 1000 kg (100%), which is cold. A cotton type pigment release agent for transfer printing paper. The pigment release agent for the cotton type cold transfer printing paper is a base light milky white liquid having a viscosity of 500 to 700 Pa s, and the flow rate of the fourth coated cup is 30 seconds at 25 °C.

Example 7

Wool (protein fiber) type fabrics are used as pigment release agents for cold transfer printing paper.

Poly[acrylic acid (styrene)-starch graft copolymer ~75%, Gas phase grade silica 0.2%,

Castor oil bowl sodium is 0.4%

Tributyl phosphate is 0.5%,

Adjust water to 100%.

In the industrial reactor, ^2.5 kg of triethanolamine, 58 kg of water and lkg of polyoxyethylene sorbitan monooleate are firstly injected into an emulsion, and lkg of sodium hydrogen sulfite and 0.5 kg of potassium persulfate are added under stirring. The temperature is raised to 50 ° C as an initiator; 340 kg of ethyl acrylate, 60 kg of acrylic acid and 100 kg of styrene are mixed and added dropwise to the initiator emulsion. After the polymerization is initiated, the system is automatically heated to 85 ° C, ie, etherification is added. Modified starch with a degree of 0.7-1.2 (hydroxyl shielded) 250kg, controlled temperature at 70~85°C^, continued reaction for lh-2h, achieving graft copolymerization of acrylic acid-styrene copolymer and starch, heavy The average molecular weight is about 22,000 Daltons. 2 kg of fumed silica and 4 kg of sodium sesame oil were added to the copolymer emulsion. After the above materials were uniformly stirred, 5 kg of tributyl phosphate was added, and finally water was adjusted to 1000 kg (100%), which was used for cold transfer printing paper. Hair pigment spacers. The pigment release agent for this type of cold transfer printing paper is a milky white liquid with a viscosity of 950 ~ HOOpa · s, and the flow rate of the 2nd cup of the Zahn Cup is 25 - 35 seconds under the condition of 25 inches. The grafting ratio is over 38%.

Example 8

Synthetic fiber (polyester, nylon and acrylic) type pigment spacer for cold transfer printing paper

Formulated by mass percentage:

Poly [(meth) acrylate-styrene]-starch graft copolymer ~ 82 %, silica 0.4%,

Castor oil bowl sodium is 0.9%

Tributyl phosphate is 0.7%,

Pyrrolidone wetting agent PH316 emulsion is 2%,

Adjust water to 100%. The poly[(meth)acrylate-styrene]-starch graft copolymer prepared in Example 2 was 820 kg, and the copolymer emulsion was added with 4 kg of vapor phase silica, 9 kg of castor oil sodium sulfate, and the above shield was evenly stirred. Then, add 2 kg of carboxypyrrolidone wetting agent PH316, 7 kg of tributyl phosphate, and finally adjust to 1000 kg (100%) with water, which is a synthetic fiber type pigment release agent for cold transfer printing paper. The pigment spacer for the synthetic fiber type cold transfer printing paper is a milky white liquid having a viscosity of ~900pa's, and the flow rate of the 2nd cup of the Zahn Cup at 25 °C is 30-40 seconds.

The PE-2 dye release agent prepared in the above examples can be applied to a paper base for use in a rotary screen printing machine, a flat screen printing machine, a gravure printing machine, a flexographic printing machine, a flatbed offset printing press, and an ink jet printer. For the transfer paper using the pigment isolating agent, the transfer printing paper printed by the above various printing and printing equipment can be completely peeled and peeled to various fabrics when it is pressed and applied with the fabric. on.

The above examples all emphasize the viscosity range below 1200 pa · s, and the flow rate of the 2nd cup of the Zahn Cup at 25 °C is 30 - 40 seconds. If the above viscosity cannot be maintained, the release of the dye on the paper base will be poor, and the dyeing rate of the product will not be improved. For example, the plasticity is poor in the printing of the concave plate, and the sharpness of the pattern should be lacking. The flow rate of the 2nd cup of the Zahn Cup is positioned at 30 - 40 seconds to ensure the thixotropic fluidity between the blade and the paper and the paste during coating. It is very difficult to apply the pigment spacer such as the lack of the above viscosity meter flow rate. Adapt to the printing conditions of the latter.

Example 9

Application of Cold Transfer Printing Paper Pigment Release Agent on Cold Transfer Printing Paper

Paper specifications: 60g single-sided writing paper, width 1800 wake (Anmu Huangshan Jinma Paper Mill)

PE - 2 pulp index: Fineness 2. 5 μ ιη, viscosity 400 ~ 550 cp, 25 °C ^ under the cup of the cup No. 2 cup flow rate ~ 45 seconds.

The PE-2 slurry was uniformly coated on the surface of the paper with a professional coater to form a pigment barrier layer. Then, by printing on the side of the paper coated with the pigment isolation layer, Form a cold transfer printing paper.

Example 10

Application of Cold Transfer Printing Paper Pigment Release Agent on Inkjet Transfer Printing Paper

Paper specifications: 60g writing paper, (Shandong Weifang Paper Mill)

Coating slurry: 97 parts of PE-2 slurry, 1 part of polyvinylpyrrolidone, 2 parts of Germany 3011 oil.

The PE-2 slurry was first treated with a homogenizer, and the fineness of the particles was measured with a fineness scraper, and the fineness was 0.25 μm. The coating method is coated with West Bay BABC-CK machine blanket, 9 g per m ² , 30-40 min per minute.

Example 11

Application of cold transfer printing paper coated with pigment release agent in flexographic printing

PE - 2 pulp index: Viscosity: 450 cps, No. 4 painted cups at 25 ° C for 45 s. The rubber blanket is used as the pressure bearing material and the knife coating method. Coating amount: 7-9 g/m ² , Huangshan Paper Company

50 - 60 g heavy web.

Example 11 '

Application of Cold Transfer Printing Paper Coated with Pigment Release Agent in Four-page Printing

The following formula is applied when applying PE-2 slurry: Viscosity: 560 cps, No. 4 coating cup flow seconds 90s under 25'C condition, single or reverse roll coating with a doctor blade. Coating amount 7-12 g

/m ² , Fujian Nanping Xingguang brand news roll paper 29-56 grams.

Example 13

Application of cold transfer printing paper coated with pigment release agent in rotary screen printing

In order to produce transfer paper for outdoor products, the Penta Screenl 25 mesh round mesh has an opening ratio of 15%, which is suitable for fine pattern printing. The printing line pressure was 1.5 kg/cm. In the application of PE-2 slurry, the following formulation was used: viscosity 950 cps, No. 4 coating cup at 25 ° C for 1 minute and 20 seconds, using a round mesh 105 mesh online coating. Coating amount 12-15 g / m ² , using Shandong Qingzhou paper mill single glue 90 g web.

Example 14 Application of cold transfer printing paper pigment release agent in cold transfer printing of cotton gauze fabric

Fabric specifications: 12x 10 cotton gauze, whiteness 74 ~ 79, gross effect >9,

PE - 2 slurry index: Viscosity HOOcp, flow rate of No. 4 coating cup at 280s at 25 °C. The fabric was padded and wetted in a NaOH alkaline agent of Baume 36.5, passed through a three-roll mill, one immersion and two rolling, the rolling ratio was ～60%, and the rolling speed was 2.5/min. The pigment prepared in Example 3 was used. The release agent (ie PE-2 slurry) has a transfer rate of approximately 95% on the fabric.

Example 15

Application of cold transfer printing paper pigment release agent in cold transfer printing of cotton corduroy fabric

Fabric specifications: 16 X 21 of 16 cotton corduroy, whiteness 73, yellowness index 6.58, gross effect > 9.8,

PE-2 slurry index: viscosity 880cp, the flow rate of No. 4 coating cup is 119s at 25°C, the fabric is wetted by padding in a mixed solution of Baume 36 NaOH and Na ₂ Si0 ₃ , through a three-roll mill, a dip Two rolling, the remnant rate is ~65%, using the PE prepared in Example 4

2 pulp pigment release agent, the transfer rate on the fabric is about 92%.

Example 16

Application of Cold Transfer Printing Paper Pigment Release Agent in Cold Transfer Printing of Pure Spinning Tencel Fabric

Fabric specifications: 21x 21 pure spinning Tencel - regenerated cellulose fiber, whiteness 76, hair effect ~10,

PE-2 plasma indicators:? Viscosity 630cp, under conditions of 25'C flow cup No. 4 finish 167s, fabric Baume 37 ^ _₃₀₄ with Na ₂ C0 ₃ solution was padded wetted mixture, through a three roll The car, one dip and two rolling, had a ranch rate of ~55%. Using the PE-2 pulp pigment release agent prepared in Example 5, the transfer rate on the fabric was about 95%.

Through the application examples of the above three cold transfer printing 3⁄4 paper pigment spacers in cold transfer printing of pure textiles, it can be seen that the use of PE pigment release agent makes the dye transfer from The transfer rate of paper transferred to the fabric is 4艮 high, reaching more than 90%, and the PE pigment release agent coating on the printing paper is properly hydrophobic, ensuring complete printing of the substrate, making the printing pattern complete and clear; Adhesion, moisture retreat and other issues; have a good pH adaptation range; dye pattern adhesion, no color loss phenomenon. Minimize the pollution of residual dyes to the environment and promote the further development of the printing and dyeing industry towards the environmental protection economy. The alkyl emulsifiers mentioned in the examples are higher fatty alcohol sulfates; such emulsifiers are more emulsifiable, but are more stable than soap emulsifiers, and are anionic and moisturizing and increasing. Dissolving function.

The paste composed of [acrylic acid]-styrene grafted with starch solves the problem of tension and balance between the hydrophobic layer and the hydrophilic layer of the barrier layer coated with the front transfer paper. The cold transfer printing paste provides barrier separation during transfer and hydrophilic printability during printing. The research invention of the present invention effectively solves the application of cold transfer printing on various fibers and the use on various printing apparatuses.

Claims

Rights request

1. A graft copolymer composed of polyacrylic acid (styrene)-styrene, which is (meth)acrylic acid, (meth)acrylic acid ester, styrene The terpolymer has a weight average molecular weight of from 2,500 to 30,000 Daltons and an average grafting ratio of from 25% to 40%. The structural formula of the graft copolymer is expressed as:

Wherein, AGU represents a structural unit constituting starch, n represents a repeating number of the structural unit, and Poly [Acryl ic acid (Acrylate)-Styrene] represents poly[acrylic acid]-styrene, and the poly[acrylic acid (ester) - Styrene] grafted at the C3 position, C2 position and C6 position of the starch molecule, and the substance grafted at the C3 position of the starch molecule is dominant

The graft copolymer according to claim 1, which is a graft copolymer of a terpolymer of acrylic acid, acrylate or styrene and starch.

The graft copolymer according to claim 1, wherein the (meth) acrylate is a CI-C10 alkyl ester of (meth)acrylic acid.

The graft copolymer according to claim 1, wherein the (meth) acrylate is propyl acrylate and/or butyl acrylate.

5. The method for preparing a graft copolymer according to any one of claims 1 to 4, comprising the following two steps: (1) controlling a monomer concentration, an initiator concentration, an emulsifier concentration, and a polymerization temperature, Producing poly[acrylic acid (styrene)-styrene]; (2) oxidizing the starch by an initiator, and grafting the poly[acrylic acid (styrene)-styrene] with the starch under the condition that the starch generates a radical, Formation of poly[acrylic acid]-styrene graft copolymer, graft ratio Between 25% and 40%.

The method according to claim 5, wherein in the step (1), (meth)acrylic acid, (meth) acrylate, and styrene or (meth)acrylic acid are used as a monomer. a monomer mixture of an ester and styrene is added to an emulsion system formed by an emulsifier polyoxyethylene sorbitan monooleate. For the above ternary system, at a temperature of 50 ° C, for the above binary system At a temperature of 60 ° C, polymerization is initiated to form poly [propionate-styrene], and the temperature of the system is automatically increased as the total amount proceeds.

The preparation method according to claim 5, wherein in the step (2),

When the temperature of the system reaches 85 °C, the modified starch with a degree of etherification of 0.7-1.2 is added, the temperature is controlled at 70-85 ° C ^, and the reaction is continued for 1-2 hours. When the system reaches the viscosity requirement, the reaction is stopped. Poly[acrylic acid]-styrene]-starch graft copolymer.

Use of the graft copolymer according to any one of claims 1 to 4 for the preparation of a pigment release agent for cold transfer printing paper.

A pigment release agent comprising the graft copolymer according to any one of claims 1 to 4, castor oil sulfate, phosphate, and silica or palygorite as a filler.

The dye release agent according to claim 9, wherein the graft copolymer contains 35 % -85 % by weight, 0.2-1.8 % of castor oil sulfate, 0.1 - 0.8 % of phosphate, and 2 parts by weight. The silica is 0.05% - 0.5% by mass or the palygorskite is 3.9 % by mass, and the balance is water.

The pigment release agent according to claim 9 or 10, which is used for a natural fiber fabric comprising cotton, wool, silk, a cellulose fiber fabric, and a cold transfer printing paper for a synthetic fiber fabric comprising polyester, nylon and acrylic. Cold transfer printing process.

12. The pigment release agent of claim 9 or 10 for use in a flexographic printing press, a printing press, Screen printing machine, inkjet printer, transfer printing paper for printing fabrics.

13. An article having a coating formed from the pigment release agent of claim 9 or 10.

14. The article of claim 13 which is a cold transfer printing paper having said coating on the surface of the paper base.