CN1477134A - Hollow polymer particle and its preparing method, paper coating composition, coating paper and mfg. method - Google Patents

Abstract

The present invention provides a kind of hollow polymer granules with good balancing property, for example gloss and coating strength and production method of said granules, paper coating composite by using said granules and coated paper. The hollow polymer granules can be obtained by using the following raw materials and processes: emulsion polymerization containing unsaturated carboxylic acid and free radical polymerizable monomer which can be copolymerized with unsaturated carboxylic acid, preparation of polymer granules, preparing core-shell polymer granules, regulating pH value of dispersion containing said core-shell polymer granules to above 7 and polymerizing unreacted monomer.

Description

Hollow polymer particle and method for making, paper coating composition, White Board and method for making

Technical field

The present invention relates to a kind of hollow polymer particle, its manufacture method is used its paper coating composition, uses the paper of said composition coating and a kind of manufacture method of this White Board.

More specifically, the present invention relates to a kind of technology, it can be produced effectively has well balanced various performances, as screening performance, gloss, coating strength, water tolerance, alkali resistance, weathering resistance and thermotolerance, and the hollow polymer particle with single-size diameter and high hollow rate, especially can in the coating of paper, fiber, leather etc., coating etc., be used as the hollow polymer particle of light scattering agent or scattering of light auxiliary agent.

In addition, the present invention relates to a kind of paper coating composition, it can obtain having well balanced performance, as whiteness, opaqueness, gloss, coating strength, print gloss and low spot performance, further, have screening performance, gloss, water tolerance, alkali resistance, weathering resistance and a stable on heating White Board; Use the White Board of said composition; Manufacture method with a kind of White Board.

Background technology

So far in fields such as the paint field of paper, fiber, leather etc., paint field, hollow polymer particle, promptly, wherein there is the polymer beads of single airtight emptying aperture to be widely used as, for example its mesopore is filled with organic microcapsule granule of various materials, or utilizes organic light scattering agent or organic scattering of light auxiliary agent of the light scattering property that is produced by the preparation hollow particle.

Manufacture method as a kind of these hollow polymer particles, following technology (JP-A-56-32513 and JP-A-63-213509) is for example disclosed: prepare a kind of particle, described particle has one respectively and comprises nuclear that the monomer system of at least one hydroxy-acid group obtains by letex polymerization and (it comprises at least a monomer by other monomer system of polymerization, can obtain Tg like this above 25 ℃, under 20 ℃, do not form coating, and the hard polymer that can in ammonia or amine, soak into) shell that obtains, neutralize this nuclear carrying out swelling with ammonia or amine, and further dry final polymkeric substance is to be formed on the single hole in the nuclear.

According to above-mentioned technology, being used to be controlled at the condition that forms hole in the nuclear is trouble and difficulty, and is difficult to the polymer beads that high productivity production has required hole.In addition, the particle of making by this technology, in the field of coating, coating etc. in the required various performances, improve though screening performance, gloss, coating strength, whiteness etc. have to a certain degree, the balance of the performance of major requirement (screening performance, gloss, coating strength, whiteness, water tolerance, alkali resistance, weathering resistance, thermotolerance etc.) can not make us satisfied completely.The ammonia of nuclear or amine neutralization and expansion are not carried out under the temperature of the Tg that surpasses the polymkeric substance that constitutes this shell, just can not get the hollow rate of enough percent by volumes.Therefore, in this production technique, high-temperature and high-pressure conditions is essential.Therefore be difficult to make shell to have high Tg and high molecular or crosslinked.The defective of the polymer beads that obtains by above-mentioned technology is, they are not suitable for requiring the occasion to mechanical pressure and ballistic patience, and need thermotolerance, the occasion of oil-proofness and chemical-resistant.

In addition, the paper coating composition of not talkative these hollow polymer particles of use has enough performances.In addition, even increase particulate content, even the hollow polymer particle of the hollow rate of low percent by volume also screening performance, gloss, coating strength, whiteness, etc. the aspect have some improvement.If descend but content surpasses certain value, various performance such as screening performance, gloss, coating strength and whiteness.On the other hand, if glue spread declines to a great extent, then can not obtain to improve.

Summary of the invention

The present invention makes according to the problems referred to above.An object of the present invention is to provide a kind of hollow polymer particle and manufacture method thereof, it has well balanced various performances such as screening performance, gloss, coating strength, water tolerance, alkali resistance, weathering resistance, thermotolerance, oil-proofness and chemical-resistant and has the single-size diameter and high hollow rate, especially can be in the coating of paper, fiber, leather etc., with in coating, be used as light scattering agent or scattering of light auxiliary agent, can be with the lesser temps manufacturing under normal pressure.

Other purpose of the present invention is made in view of the above problems, provide a kind of and have well balanced various performances such as whiteness, opaqueness, gloss, coating strength, low spot performance, and further have the paper coating composition of the White Board of performances such as good screening performance, water tolerance, alkali resistance, weathering resistance, oil-proofness, chemical-resistant, use the manufacture method of White Board and a kind of this White Board of this paper coating composition.

The present invention is described below.

1. the manufacture method of a hollow polymer particle comprises

The emulsion polymerization step of preparation polymer beads (A), the monomer (a) that can form with the free radical polymerization monomer (a-2) (total amount of above-mentioned (a-1) and above-mentioned (a-2) is set at 100 weight %) of above-mentioned unsaturated carboxylic acid (a-1) copolymerization of the unsaturated carboxylic acid (a-1) of polymerization 5-80 weight % and 20-95 weight %

The emulsion polymerization step of preparation polymer beads (B), at 5-1, the part of polymerization 100 weight parts monomers (b) under the existence of the above-mentioned polymer beads of 000 weight part (A), wherein comprise the unsaturated carboxylic acid (b-1) of 0-20 weight % and 80-100 weight % can with the free radical polymerization monomer (b-2) (total amount of above-mentioned (b-1) and above-mentioned (b-2) is set at 100 weight %) of above-mentioned unsaturated carboxylic acid (b-1) copolymerization, prepare core/shell type polymer beads (B) like this, the surface coverage of wherein above-mentioned polymer beads (A) has the shell of the unreacted monomer component that comprises the polymeric constituent that obtains by the above-mentioned monomer of a polymerization part (b) and above-mentioned monomer (b)

Expansion step will comprise the above step of pH regulator to 7 of the dispersion of above-mentioned polymer beads (B) with volatile alkali, neutralize like this and expand above-mentioned polymer beads (B) and

The polymerization procedure of the above-mentioned unreacted monomer component of polymerization.

2. according to the manufacture method of above 1 hollow polymer particle, wherein above-mentioned polymeric constituent and the weight ratio of above-mentioned unreacted monomer component in above-mentioned shell are 99/1-50/50.

3. according to the manufacture method of above 1 hollow polymer particle, wherein above-mentioned shell is by at first once adding the above-mentioned monomer (b) that part or all will become above-mentioned polymeric constituent, and letex polymerization subsequently should reinforced monomer and make.

4. according to the manufacture method of above 3 hollow polymer particle, the wherein above-mentioned monomer (b) that once adds is esters of unsaturated carboxylic acids and/or ethene aromatic substance in 100 weight % more than the 50 weight % of all above-mentioned monomers (b).

5. according to the manufacture method of above 3 hollow polymer particle, the wherein above-mentioned monomer (b) that once adds is 10/1-1/10 with the weight ratio of above-mentioned polymer beads (A).

6. according to the manufacture method of above 1 hollow polymer particle, wherein above-mentioned free radical polymerization monomer (b-2) comprises a kind of crosslinkable free radical polymerization monomer, and the content of above-mentioned crosslinkable free radical polymerization monomer is based on below the 50 weight % of all above-mentioned free radical polymerization monomers (b-2) of 100 weight %.

7. according to the manufacture method of above 1 hollow polymer particle, the temperature of wherein above-mentioned dispersion when above-mentioned polymer beads (B) is neutralized and expands is set in below the second-order transition temperature (Tg) of above-mentioned polymeric constituent.

8. according to the manufacture method of above 1 hollow polymer particle, during the emulsion polymerization of wherein above-mentioned monomer (b), by the above-mentioned free radical polymerization monomer of polymerization (b-2) only, and after the above-mentioned monomer of 10-35 weight % (b-2) is finished polymerization, the above-mentioned unsaturated carboxylic acid of copolymerization (b-1) again.

9. the hollow polymer particle of making by above 1 manufacture method.

10. according to above 9 hollow polymer particle, wherein hollow rate is 50-99%.

11. a paper coating composition is characterized in that comprising hollow polymer particle (X) and the 0-99.9 weight % pigment (Z) and/or the binding agent (Y) of the basis above 9 of 0.1-100 weight %, (above-mentioned (X), (Y) and total amount (Z) be 100 weight %).

12. the paper coating composition according to above 11, the hollow rate of wherein above-mentioned hollow polymer particle (X) is 50-99%.

13. a paper coating composition is characterized in that comprising and has hollow rate percent by volume 50-99% and median size 300-5, the hollow polymer particle of 000nm.

14. the paper coating composition according to above 13, wherein the thickness of the shell of above-mentioned hollow polymer particle is 30-200nm.

15. the paper coating composition according to above 13, wherein above-mentioned hollow polymer particle are the hollow particles of above 9 records.

16. the paper coating composition according to above 13 comprises with solids component and converts as the above-mentioned hollow polymer particle of 0.5-99.5 weight %, 0.5-99.5 weight % binding agent and the 0-99 weight % pigment and/or the thickening material of the total component of 100 weight %.

17. White Board, comprise body paper and on the single or double of above-mentioned body paper, form and by the coating that hollow polymer particle and binding agent constitute, the volume hollow rate that it is characterized in that above-mentioned hollow polymer particle is that 50-99% and average particulate diameter are 300-5000nm.

18. the manufacture method of a White Board is characterised in that the paper coating composition with above 13 records is applied on the body paper, makes that the glue spread of above-mentioned composition after the said composition drying is 0.3-30g/m ²

The present invention can provide a kind of technology, it can be produced effectively has excellent coating, have well balanced coating performance such as screening performance, whiteness, opaqueness, gloss, coating strength, water tolerance, alkali resistance, weathering resistance, thermotolerance and chemical-resistant, and the hollow polymer particle with single-size diameter and high hollow rate, especially can in purposes such as the coating of paper, fiber, leather etc., coating, be used as the hollow polymer particle of light scattering agent or scattering of light auxiliary agent.

Hollow polymer particle of the present invention can be used for the various uses outside above-mentioned, coating for example, printing ink, with the reagent that deals with fiber or leather, as the dry load of ink jetting paper, the filler in the paper technology, cover pigment as opaquing fluid or the height of revising band, as the raw material of microcapsule with as the intermediary material of the toning agent of electrofax.

Hollow polymer particle of the present invention also can be used for utilizing the product of air adiabatic performance, for example, and as thermal printer paper, the thermal insulation layer of the heat-sensitive layer undercoat of thermal transfer printer paper or temperature-sensitive paper, or can be used as and utilize product that air lightens for example, resin, cement and concrete additive.

In addition, hollow polymer particle of the present invention can add in semiconductor-encapsulating material etc. to utilize the low-dielectric energy of air.

Because paper coating composition of the present invention comprises the hollow rate that has in specialized range and the hollow polymer particle of average particulate diameter, can obtain a kind of White Board with well balanced printing performance such as whiteness, opaqueness, gloss, coating strength and print gloss.

If comprise the binding agent of requirement ratio, this paper coating composition can obtain having the more White Board of good surface intensity, opaqueness, gloss etc.

In addition, if comprise pigment or other additive, this paper coating composition can obtain having the White Board of better printing performance such as whiteness, opaqueness, gloss, coating strength and print gloss.

If the use hollow polymer particle made of technology can obtain the bigger hollow polymer particle of hollow rate according to the rules.

Thereby, can obtain having the more White Board of premium properties by using above-mentioned paper coating composition to use with the regulation glue spread.

If be coated with, can obtain having the more White Board of premium properties by the noncontact coating process.

Embodiment

Below specify the present invention.

1. the manufacture method of hollow polymer particle

Hollow polymer particle of the present invention can be made according to following technology:

Specific monomer (a) letex polymerization is become the step of polymer beads (A),

The step of preparation core/shell type polymer beads (B), wherein the surface coverage of polymer beads (A) has the shell of the unreacted monomer component that comprises the polymeric constituent that obtains by polymerization specific monomer (b) and monomer (b),

Use volatile alkali will comprise the above step of pH regulator to 7 of the required product of polymer beads (B), neutralize like this and inflated polymer composition granule (B) and

Unreacted monomer component is aggregated into the step of final hollow polymer particle (X).

The following specifically describes each step in the above-mentioned technology.

(1) preparation of polymer beads (A)

At first, letex polymerization is prepared title polymer particle (A) like this by unsaturated carboxylic acid (a-1) [below be called " monomer (a-1) "] and the monomer (a) that can form with the free radical polymerization monomer (a-2) of monomer (a-1) copolymerization [below be called " monomer (a-2) "].The kind of the dispersion medium that use this moment is not particularly limited, and uses aqueous medium usually.

This aqueous medium is water normally.Also can use the water medium that contains water-miscible organic solvent (for example, ethanol, methyl alcohol, acetone etc.).

As the example of monomer (a-1), comprise single-or dicarboxylic acid as the acid anhydrides of (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid and methylene-succinic acid etc. and dicarboxylic acid etc.Consider particulate stability, preferred (methyl) vinylformic acid and methylene-succinic acid.More preferably (methyl) vinylformic acid.These materials can be separately or two or more mix and use.

As the example of monomer (a-2), comprise esters of unsaturated carboxylic acids, ethene aromatic substance and other non-crosslinked free radical polymerization monomer.These materials can be separately or two or more mix and use.In these compounds, preferred esters of unsaturated carboxylic acids.Preferably, be esters of unsaturated carboxylic acids more than the 50 weight % of monomer (a-2).If monomer (a-2) comprises the esters of unsaturated carboxylic acids that is lower than 50 weight %, the shape of final hollow polymer particle becomes and twists and hollow rate decline.

Example as esters of unsaturated carboxylic acids comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA etc.These materials can be separately or two or more mix and use.

As the example of ethene aromatic substance, comprise vinylbenzene, alpha-methyl styrene etc.These materials can be separately or two or more mix and use.

The example of other non-crosslinked free radical polymerization monomer comprises (methyl) vinyl cyanide, vinyl-acetic ester, N, N-dimethyl (methyl) acrylamide etc.These materials can be separately or two or more mix and use.

As the part of monomer (a-2), can use crosslinkable monomers.The example of crosslinkable monomers comprises divinyl, isoprene, Vinylstyrene, two (methyl) vinylformic acid glycol ester etc.These materials can be separately or two or more mix and use.The feeding quantity of crosslinkable monomers is preferably below the 5 weight % of monomer (a) total amount, more preferably 0.2-2 weight %.If the amount of crosslinkable monomers surpasses 5 weight %, the expansion deficiency of volatile alkali, hollow rate step-down like this, the degradation of covering property, whiteness and gloss and so on.

Monomer (a-1) and the content of monomer (a-2) in the monomer that is fed in raw material (a) are as follows:

The total amount of monomer (a-1) and monomer (a-2) is as 100%, and it is respectively 5-80 weight % and 20-95 weight %, preferably is respectively 10-60 weight % and 40-90 weight %, more preferably is respectively 20-50 weight % and 50-80 weight %.

If the amount of monomer (a-1) is lower than 5 weight %, the expansion deficiency of volatile alkali, hollow rate step-down like this.As a result, the degradation of screening performance, whiteness and gloss and so on, inadvisable.On the other hand, if the amount of monomer (a-1) surpasses 80 weight %, the polyreaction stability decreases of monomer (a).Be difficult to evenly cover the polymkeric substance of monomer (b), the become distortion and inadvisable of the shape of final hollow polymer particle at this particle surface layer.

The method of letex polymerization monomer (a) is not particularly limited in dispersion medium.For example, monomer can once add and polymerization, also can add and polymerization continuously.In order stably to obtain having the particle of single-size diameter, the preferred latter.The preparation of polymer beads (A) can be undertaken by polyreaction in single step or the reaction of the multistep polymerization in two or more steps.Monomer can carry out the seeded emulsion polymerization reaction in the presence of seed grain.In order stably to obtain having the particle of single-size diameter, seed grain is preferably the SP value (solubility parameter) and the approaching particle of monomer (a) of the polymkeric substance that wherein constitutes seed grain.

Emulsifying agent can be used for the emulsion polymerization of monomer (a).The example of emulsifying agent comprises anion surfactant, nonionogenic tenside, cats product, amphoterics, organic suspension liquid protective material etc.Consider particulate stability, preferred anionic tensio-active agent, nonionogenic tenside and organic suspension liquid protective material.These emulsifying agents can be separately or two or more mix and use.

As examples of anionic surfactants, comprise sylvate, as the sylvite of sylvic acid and the sodium salt of sylvic acid, the sodium or the sylvite of aliphatic acid, as potassium oleate, potassium laurate, sodium laurate, sodium stearate and potassium stearate, the sulfuric acid of fatty alcohol, as Sodium Lauryl Sulphate BP/USP, alkyl allyl sulphonic acid such as Sodium dodecylbenzene sulfonate etc.These anion surfactants can be separately or two or more mix and use.

Example as nonionogenic tenside.Comprise alkane ester, alkyl oxide, alkyl phenyl ether of polyoxyethylene glycol etc.These nonionogenic tensides can be separately or two or more mix and use.

As the protectant example of organic suspension liquid; comprise hydrophilic synthetic macromolecule material; as polyacrylic acid, polymethyl acrylic acid, polyvinylsulfonic acid, polyvinyl alcohol, polyvinylpyrrolidone and polyoxyethylene glycol; natural hydrophilic macromolecular material; as gelatin and water soluble starch; hydrophilic semi-synthetic macromolecular material is as carboxymethyl cellulose etc.These organic suspension liquid protective materials can be separately or two or more mix and use.

As the example of cats product, comprise aliphatic amine salt, aliphatic quaternary ammonium salt etc.These materials can be separately or two or more mix and use.

As the example of amphoterics, comprise carboxybetaine type tensio-active agent, aminocarboxylate etc.

The example of initiators for polymerization that is used for the emulsion polymerization of monomer (a) comprises:

(i) redox initiator, for example, organic hydroperoxide, as cumene hydroperoxide, diisopropyl benzene hydroperoxide, to menthane hydroperoxide and tertbutanol peroxide, with reductive agent as, any combination of sacchariferous tetra-sodium prescription, sulfoxylate prescription, sacchariferous tetra-sodium prescription and sulfoxylate prescription mixing formula and formaldehyde resin prescription

(ii) persulphate, as Potassium Persulphate and ammonium persulphate,

(iii) Diisopropyl azodicarboxylate,

(iv) organic hydroperoxide, as benzoyl peroxide and lauroyl peroxide, etc.

Consider the homogeneity of particulate stability and particle diameter, preferred persulphate, as Potassium Persulphate and ammonium persulphate, Diisopropyl azodicarboxylate and benzoyl peroxide.

Polymeric reaction temperature during polymerization single polymerization monomer (a) is preferably 5-95 ℃, more preferably 50-90 ℃.If polymeric reaction temperature is lower than 5 ℃, unsaturated carboxylic acid reactive low, it is unstable that so final particle can become.On the other hand, if temperature surpasses 95 ℃, it is unstable that particle can become.

Final polymer beads (A) is a kind of alkali swelling nuclear particle.The average particulate diameter of polymer beads (A) is preferably 0.1-2 μ m, more preferably 0.2-2 μ m.

(2) preparation of polymer beads (B)

Polymer beads (B) passes through at 5-1,000 weight part, preferred 7-100 weight part and more preferably under the existence of 10-50 parts by weight polymer particle (A), letex polymerization 100 weight parts monomers (b) and be made for a kind of core/shell type polymer beads, wherein the surface coverage of polymer beads (A) has the shell of the unreacted monomer component that comprises the polymeric constituent that obtains by polymerization part monomer (b) and monomer (b).

If the amount of polymer beads (A) is lower than 5 weight parts, the formation of hole in final hollow polymer particle (X) becomes not enough and causes when forming coating performances such as screening performance, whiteness, gloss bad.On the other hand, if the amount of polymer beads (A) surpasses 1,000 weight part, polyreaction stability decreases.In addition, stand that volatile alkali is handled and the polymer beads of heat treated breaks and be out of shape fragmentation, hollow rate decline.

Monomer (b) is by unsaturated carboxylic acid (b-1) [below be called " monomer (b-1) "] and can form with the free radical polymerization monomer (b-2) of monomer (b-1) copolymerization [below be called " monomer (b-2) "].

As the example of monomer (b-1), comprise single-or dicarboxylic acid as the acid anhydrides of (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid and methylene-succinic acid, dicarboxylic acid etc.Consider particulate stability, preferred (methyl) vinylformic acid and methylene-succinic acid.More preferably (methyl) vinylformic acid.These materials can be separately or two or more mix and use.

As the example of monomer (b-2), comprise esters of unsaturated carboxylic acids, ethene aromatic substance and other non-crosslinked free radical polymerization monomer.These materials can be separately or two or more mix and use.In these compounds, the optimal ethylene aromatic substance.Preferably, 50 weight % of monomer (b-2) total amount are above to be the ethene aromatic substance, as vinylbenzene.If monomer (b-2) comprises the ethene aromatic substance that is lower than 50 weight %, the specific refractory power of polymkeric substance descends, and causes whiteness, and opaqueness and gloss may be not enough.

Example as esters of unsaturated carboxylic acids comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA etc.These materials can be separately or two or more mix and use.

As the example of ethene aromatic substance, comprise vinylbenzene, alpha-methyl styrene etc.These materials can be separately or two or more mix and use.

The example of other non-crosslinked free radical polymerization monomer comprises (methyl) vinyl cyanide, vinyl-acetic ester, N, N-dimethyl (methyl) acrylamide etc.These materials can be separately or two or more mix and use.

Monomer (b-2) can comprise the crosslinkable free radical polymerization monomer.Swelling, decomposition or the similar effect that can cause and keep the shape of final hollow particle like this at heat, mechanical stress, by solvent or chemical.The example of crosslinkable free radical polymerization monomer comprises Vinylstyrene, trivinylbenzene, Dicyclopentadiene (DCPD), divinyl, isoprene, allyl glycidyl ether, (methyl) glycidyl acrylate, two (methyl) vinylformic acid glycol ester etc.Preferred Vinylstyrene and two (methyl) vinylformic acid glycol ester.These materials can be separately or two or more mix and use.

If use the crosslinkable free radical polymerization monomer, monomeric feeding quantity is preferably based on below the 50 weight % of monomer (b-2) total amount and more preferably 0.1-30 weight %.If the amount of crosslinkable free radical polymerization monomer surpasses 50 weight %, it is not enough that hollow rate becomes.The total amount of monomer (b) is as 100%, and so monomeric feeding quantity is preferably below 20 weight parts, more preferably the 0.1-10 weight part.

Monomer (b-1) and the content of monomer (b-2) in the monomer that is fed in raw material (b) are as follows:

Total amount in monomer (b-1) and monomer (b-2) is 100 weight %, the amount of monomer (b-1) and monomer (b-2) is respectively 0-20 weight % and 80-100 weight %, preferably be respectively 0.1-10 weight % and 90-99.9 weight %, more preferably be respectively 0.2-5 weight % and 95-99.8 weight %.

If the amount of monomer (b-1) surpasses 20%, polyreaction stability significantly descends.In addition, stand the final hollow polymer particle distortion and the hollow rate decline of volatile alkali processing and heat treated.

Be not particularly limited the method for letex polymerization monomer (b), identical method in the time of can using with polymer beads (A).

For the covered structure that makes shell is complete, preferably at first part or all to be formed the once reinforced and monomer that will feed in raw material of the monomer (b) of polymeric constituent and in the presence of polymkeric substance (A), carry out letex polymerization.At this moment, once the monomer of Jia Ruing (b) is preferably 10/1-1/10 with the weight ratio of polymer beads (A), more preferably 5/1-1/5.If ratio surpasses 10/1, stability is not enough.If ratio is lower than 1/10, the covering of polymer beads (A) is not enough and final hollow polymer particle distortion, and hollow rate descends.

Particularly preferably be, at first once Jia Liao monomer (b) is the ethene aromatic substance, as vinylbenzene and esters of unsaturated carboxylic acids as (methyl) methyl acrylate.

In order to obtain the hollow polymer particle of high hollow rate, preferred polymerization free radical polymerisable monomer (b 1) at first only, and at common 10-35 weight %, preferred 20-30 weight % monomer (b-2) is finished after the polymerization, and remaining described free radical polymerization monomer (b-2) and described unsaturated carboxylic acid (b-1) are carried out polymerization.

In the shell of polymer beads (B), the weight ratio that obtains polymeric constituent and unreacted monomer component by polymerization single polymerization monomer (b) is preferably 99/1-50/50, more preferably 97/3-80/20.If the weight of polymeric constituent surpasses 99, need in the rising volatile alkali and the time temperature to improve hollow rate, inadvisable.In addition, if the weight of polymeric constituent is below 50, temperature in neutralization and the expansion process and pH are not easy control.Therefore, final hollow polymer particle distorts.

In order to improve whiteness, opaqueness and gloss, the second-order transition temperature (Tg) that constitutes the polymkeric substance of polymer beads (B) shell is more than 50 ℃, and is preferred more than 70 ℃ and more preferably more than 100 ℃.The particle diameter of polymer beads (B) is preferably 0.15-4 μ m, more preferably 0.25-3 μ m.

(3) preparation of hollow polymer particle (X)

Wherein filling the hollow polymer particle (X) (aqueous particulate) of water medium makes like this: will comprise with volatile alkali such as ammonia and amine more than the pH regulator to 7 of dispersion of core/shell type polymkeric substance (B), neutralize like this and expand this polymer beads, heating as required afterwards, the last unreacted monomer component of polymerization.

The temperature of dispersion when neutralization and inflated polymer composition granule (B) depends on the amount of unreacted monomer component in polymer beads (B) shell, preferably is no more than the second-order transition temperature (Tg) of the above-mentioned polymeric constituent that constitutes polymer beads (B) shell.If neutralization and expand is being carried out surpassing under the temperature of Tg, endorsing breaks passes shell and goes out to the outside.

Because the polymeric constituent that obtains by polymerization single polymerization monomer (b) is a kind of component of wherein saturable volatile alkali, the component that constitutes polymer beads (A) neutralizes by soaking into of volatile alkali.Be accompanied by neutralization, the component that constitutes polymer beads (A) significantly absorbs water.

After polymer beads (B) neutralization was expanded, the unreacted monomer component polymerization that is present in the shell obtained aqueous particulate.The concentration of monomer in dispersion that stays after unreacted monomer component polyreaction is preferably 3, below the 000ppm, and more preferably 1, below the 000ppm and most preferably below the 300ppm.If monomer keeps 3 in dispersion, the content that 000ppm is above, the rigidity deficiency of the shell of hollow polymer particle (X), the distortion of hollow polymer particle (X) easy deformation.

For the unreacted monomer component in the shell of this neutralization of abundant polymerization and inflated polymer composition granule (B), can add initiators for polymerization, polyreaction initiation auxiliary agent, reductive agent etc.

The example of initiators for polymerization comprises:

(i) redox initiator, organic hydroperoxide for example, as cumene hydroperoxide, diisopropyl benzene hydroperoxide, to menthane hydroperoxide and tertbutanol peroxide, and reductive agent, mixing formula as sacchariferous tetra-sodium prescription, sulfoxylate prescription, sacchariferous tetra-sodium prescription and sulfoxylate prescription, any combination with the formaldehyde resin prescription

(ii) persulphate, as Potassium Persulphate and ammonium persulphate,

(iii) Diisopropyl azodicarboxylate,

(iv) organic hydroperoxide, as benzoyl peroxide and lauroyl peroxide, etc.

Consider hyperergy, wherein preferred tertbutanol peroxide mixes the system of using with formaldehyde resin.

The neutralization and inflated polymer composition granule (B) afterwards, free radical polymerization monomer can newly add to carry out polymerization.Like this, finally polymkeric substance can become the part of the shell of hollow polymer particle (X).In this case, above-mentioned initiators for polymerization etc. preferably adds together.

The dry aqueous particulate that generates, the method that becomes hollow particle is not particularly limited.The example of drying means is included in the spray drying process under temperature 135-155 ℃, in the tray drying method of temperature 50-70 ℃ of following use hot-air drier, and the methods such as fluidised bed drying method under temperature 15-70 ℃.

According to the present invention, can be made into a kind of particle diameter 0.2-8 μ m, have single hole, hollow rate is 20-99%, preferred 50-99%, more preferably 51-99%, preferred again 56-99%, further preferred again 60-99%, especially preferred 63-98%, especially more preferably 65-98%, especially further more preferably 68-98% and the most preferably hollow polymer particle of 70-98% (X).Preferably can make a kind of particle diameter 300-5000nm, have the hollow polymer particle that single hole and hollow rate are 60-99% (X) by above-mentioned technology.

In addition, can be made into that a kind of to have hollow rate be 56-99%, preferred 60-99%, more preferably 63-98%, preferred again 65-98% and further more preferably 68-98% and thickness of the shell 20-220nm, preferred 20-190nm, more preferably 30-180nm and the hollow polymer particle of preferred 30-150nm again.Can obtain having high hollow rate and the thin hollow polymer particle of thickness of the shell.

If be applied to paper coating composition, final aqueous particulate itself can enter paper coating composition and need not be dry.This aqueous particulate can be carried out drying so that as the volatilization of the water-bearing media of dispersion medium, and this dried particles can be used as the powdery hollow particle that vapors away water medium in addition from its inside.If use the paper coating composition that comprises aqueous particulate, when coating etc. were dry, water-bearing media evaporated and the formation hole.

2. paper coating composition and coating composition

(1) paper coating composition of first aspect present invention

The paper coating composition of first aspect present invention comprises the hollow polymer particle of making by above-mentioned technology (X).Below, will be called " hollow polymer particle (X1) " according to the hollow polymer particle of first aspect present invention.

Hollow rate according to the hollow polymer particle (X1) of first aspect present invention is 20-99%, preferred 50-99%, more preferably 51-99%, preferred again 56-99%, further more preferably 60-99%, especially preferred 63-98%, especially more preferably 65-98%, especially further more preferably 68-98% and most preferably 70-98%.Be lower than 20% hollow rate and cause performances such as insufficient opaqueness, whiteness, gloss.On the other hand, if hollow rate surpasses 99%, mechanical stability descends, particle distortion or broken when preparation composition or coating said composition like this.The average particulate diameter of hollow polymer particle (X1) can be 200-8000nm, preferred 300-5000nm, more preferably 500-3000nm and preferred again 700-2000nm.If average particulate diameter is lower than 200nm, degradation such as opaqueness, whiteness, gloss white coloured paper.On the other hand, if average particulate diameter surpasses 8000nm, mechanical stability descends.

The thickness of the shell of hollow polymer particle (X1) can be 20-220nm, preferred 20-190nm, more preferably 30-180nm and preferred again 30-150nm.Can obtain light paper coating composition like this.Hollow polymer particle can use under this hole is filled with the state of water-bearing media such as water.Be called aqueous particulate below being in the particle of this state.In addition, hollow polymer particle can use the aqueous particulate drying with the dried, hollow graininess of removing water in the particle.In this specification sheets and claims, hollow polymer particle is represented two kinds of aqueous particulate and dried, hollow particles.

The content of hollow polymer particle (X1) is in the summation 100 weight % of hollow polymer particle (X1), binding agent (Y) and pigment (Z), be 0.1-100 weight %, preferred 1-95 weight %, more preferably 3-50 weight %, 5-30 weight % most preferably, and based on the summation 100 weight part meters of weight hollow polymer particle (X1) and pigment (Z), the content of hollow polymer particle (X1) is the 0.1-100 weight part, preferred 1-90 weight part, more preferably 1-20 weight part.

Composition of the present invention can comprise pigment (Z) and/or binding agent (Y).

Binding agent (Y) is not particularly limited, as long as it is as the binding agent of paper coating etc.The example of binding agent comprises natural adhesive, as the starch and the casein of starch, modification, synthetic adhesive such as styrene-butadiene copolymer; The styrene-butadiene copolymer of modification, the acrylic copolymer of the styrene-butadiene copolymer of for example carboxy-modified styrene-butadiene copolymer, amine modification and the styrene-butadiene-copolymer of hydroxyl modification, polyvinyl acetate, acrylate copolymer, sovprene, polyvinyl alcohol and modification, for example carboxy-modified acrylic copolymer, the acrylic copolymer of the acrylic copolymer of amine modification and oh group modification.These binding agents can be separately or two or more mix and use.

Wherein, the particularly carboxy-modified styrene-butadiene copolymer of the preferred styrene-butadiene copolymer that uses modification separately or mix use with natural adhesive such as starch or casein.

As above-mentioned binding agent, can use the binding agent that in latex, comprises as solids content, maybe can use powder binder.

The content of binding agent (Y) is preferably 1-50 weight %, more preferably 3-35 weight % in component (X1), (Y) and the 100 weight % of summation (Z).And the content of binding agent (Y) is the 1-50 weight part, preferred 5-30 weight part in the component (X1) and (Z) summation 100 weight parts of solid shape content.

The example of pigment (Z) comprises pigment dyestuff and mineral dye.The example of mineral dye comprises kaolin clay, talcum, barium sulfate, titanium oxide (rutile and anatase octahedrite), lime carbonate, aluminium hydroxide, zinc oxide and satin white.These materials can be separately or two or more mix and use.

The example of pigment dyestuff comprises styryl, phenylethylene/butadiene base and styrene/acrylic component base pigment, solid plastic pigment, urea resin particle etc.These materials can be separately or two or more mix and use.

The content of pigment (Z) is with component (X1), (Y) and the meter of summation 100 weight % (Z) be preferably 1-95 weight %, more preferably 60-85 weight %.And the content of pigment (Z) is in (X1) and 100 weight parts of summation (Z), and preferred 70-90 weight part is the 50-99 weight part more preferably.

Composition of the present invention, in component (X1)/Y and summation 100 weight % (Z), comprise [1] 0.1-100 weight % hollow polymer particle (X1) and 0-99.9 weight % pigment (Z) and/or binding agent (Y), preferably [2] 1-95 weight % hollow polymer particle (X1) and 5-99 weight % pigment (Z) and/or binding agent (Y), more preferably [3] 3-50 weight % hollow polymer particle (X1) and 50-93 weight % pigment (Z) and/or binding agent (Y) and preferred again [4] 5-30 weight % hollow polymer particle (X1) and 70-95 weight % pigment (Z) and/or binding agent (Y).If the content of hollow polymer particle (X1) is lower than 0.1 weight %, it is not enough that whiteness, the performance of opaqueness and gloss and so on become.

Under the situation of above-mentioned [1], the content of pigment (Z) and binding agent (Y) is respectively 0-99.9 weight % and 0-98.9 weight %.Under the situation of above-mentioned [2], the content of pigment (Z) and binding agent (Y) is respectively 3-97 weight % and 2-96 weight %.Under the situation of above-mentioned (3), the content of pigment (Z) and binding agent (Y) is respectively 47-85 weight % and 3-37 weight %.Under the situation of above-mentioned [4], the content of pigment (Z) and binding agent (Y) is respectively 60-85 weight % and 10-25 weight %.

Various additives can add in the composition of the present invention as required.The example of additive comprises thickening material, dispersion agent, defoamer, water-resisting agent, lubricant etc.

The example of thickening material (W) comprises starch, casein, carboxy-modified Mierocrystalline cellulose, propylene soda acid thickening material.These materials can be separately or two or more mix and use.The add-on of thickening material (W) is preferably below the 3 weight %, preferred 0.05-2 weight %, and more preferably 0.05-1 weight % is 100 weight in the summation of hollow polymer particle (X1), binding agent (Y), pigment (Z) and thickening material (W).

The example of dispersion agent comprises trisodium phosphate, Sodium hexametaphosphate 99, poly carboxylic acid sodium etc.These materials can be separately or two or more mix and use.The add-on of dispersion agent is preferably the 0.01-2 weight part in summation 100 weight parts of hollow polymer particle (X1) and pigment (Z), and more preferably 0.05-1 weight part is with solid content meter.

The example of lubricant comprises the higher aliphatic hydrochlorate, as calcium stearate, calcium palmitate and calcium oleate, polyethylene wax etc.These materials can be separately or two or more mix and use.The add-on of lubricant is preferably the 0.01-2 weight part based on the summation of hollow polymer particle of 100 weight parts (X1) and pigment (Z), and more preferably 0.05-1 weight part is with solid content meter.

The example of defoamer comprises polyoxyethylene glycol aliphatic series acid esters, phosphoric acid ester, silicone oil etc.These materials can be separately or two or more mix and use.The add-on of defoamer is preferably the 0.01-2 weight part that adds up to based on the hollow polymer particle of 100 weight parts (X1) and pigment (Z), and more preferably 0.05-1 weight part is with solid content meter.

Under the described condition of embodiment, the performance of the White Board that the composition of use first aspect present invention is made is as follows: gloss: 70-83, opaqueness: 88-95, thermotolerance: 0.1-5, whiteness: 80-87.

If use its hollow polymer particle (X1), pigment (Z) and binding agent (Y) content to be respectively 5-30 weight % based on 100 weight % components (X1), (Z) and summation (Y), the composition of 60-85 weight % and 10-25 weight %, the performance of gained White Board is as follows: gloss: 70-83, opaqueness: 88-95, thermotolerance: 0.1-5, whiteness: 80-87.

(2) paper coating composition of second aspect present invention

It is 50-99% that the composition of second aspect present invention comprises its hollow rate, preferred 51-99%, more preferably 56-99%, preferred again 60-99%, further more preferably 63-98%, especially preferred 65-98%, especially more preferably 68-98% and the most preferably hollow polymer particle of 70-98%.Be called " hollow polymer particle (X2) " below the above-mentioned hollow polymer particle.

The average particulate diameter of hollow polymer particle (X2) can be 300-5000nm, preferably 500-3000nm and more preferably 700-2000nm.

The thickness of the shell of hollow polymer particle (X2) can be 20-220nm, preferred 20-190nm, more preferably 30-180nm and preferred again 30-150nm.Can obtain light paper coating composition like this.Hollow polymer particle (X2) can be used as aqueous particulate or the dry dried, hollow particle of removing internal moisture of aqueous particulate uses.

The material that constitutes the hollow polymer particle (X2) of second aspect present invention is not particularly limited, comprise the multipolymer that the monomer (b) of monomer (b-1) and monomer (b-2) obtains but be preferably by polymerization, or above-mentioned multipolymer and the mixture of polymers that obtains by polymerization single polymerization monomer (b-1) or monomer (b-2).

That the example of monomer (b-1) comprises is single-or dicarboxylic acid as the acid anhydrides of (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid and methylene-succinic acid, dicarboxylic acid etc.Consider particulate stability, (methyl) vinylformic acid and methylene-succinic acid are preferred.(methyl) vinylformic acid is preferred.These materials can be separately or two or more mix and use.

The example of monomer (b-2) comprises esters of unsaturated carboxylic acids, ethene aromatic substance and other non-crosslinked free radical polymerization monomer.These materials can be separately or two or more mix and use.In these compounds, the ethene aromatic substance is preferred.Preferably, monomer (b-2) comprises 50 weight % above ethene aromatic substance such as vinylbenzene.If monomer (b-2) comprises the ethene aromatic substance that is lower than 50 weight %, the specific refractory power of polymkeric substance descends, and whiteness, opaqueness and gloss may be not enough like this.

The example of esters of unsaturated carboxylic acids comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA etc.These materials can be separately or two or more mix and use.

The example of ethene aromatic substance comprises vinylbenzene, alpha-methyl styrene etc.These materials can be separately or two or more mix and use.

The example of other non-crosslinked free radical polymerization monomer comprises (methyl) vinyl cyanide, vinyl-acetic ester, N, N-dimethyl (methyl) acrylamide etc.These materials can be separately or two or more mix and use.

Monomer (b-2) can comprise the crosslinkable free radical polymerization monomer.Swelling, decomposition or the similar effect that can cause at heat, mechanical stress, solvent or chemical and keep the shape of final hollow particle like this.The example of crosslinkable free radical polymerization monomer comprises Vinylstyrene, trivinylbenzene, Dicyclopentadiene (DCPD), divinyl, isoprene, allyl glycidyl ether, (methyl) glycidyl acrylate, two (methyl) vinylformic acid glycol ester etc.Vinylstyrene and two (methyl) vinylformic acid glycol ester is especially preferred.These materials can be separately or two or more mix and use.

If use the crosslinkable free radical polymerization monomer, this monomeric feeding quantity is preferably based on below the 50 weight % of monomer (b-2) total amount and more preferably 0.1-30 weight %.If the amount of crosslinkable free radical polymerization monomer surpasses 50 weight %, it is not enough, inadvisable that hollow rate becomes.And monomeric feeding quantity is preferably below 20 weight parts, and more preferably 0.1-10 weight part is based on the total amount 100 weight % meter of monomer (b).

Monomer (b-1) and the content of monomer (b-2) in the monomer that is fed in raw material (b) are as follows: the amount of monomer (b-1) and monomer (b-2) is respectively 0-20 weight % and 80-100 weight %, preferably be respectively 0.1-10 weight % and 90-99.9 weight %, more preferably be respectively 0.2-5 weight % and 95-99.8 weight %, the total amount of monomer (b-1) and monomer (b-2) is set at 100 weight %.

If the amount of monomer (b-1) surpasses 20%, the polyreaction stability decreases.In addition, stand the final hollow polymer particle distortion and the hollow rate decline of volatile alkali processing and heat treated.Be not particularly limited the manufacture method of hollow polymer particle (X2).For example, the manufacture method of hollow polymer particle (X) can be used as the manufacture method of producing hollow polymer particle (X2) in above-mentioned 1.

Paper coating composition of the present invention further comprises binding agent and pigment and/or thickening material.Binding agent, pigment and thickening material can use according to the explanation in first aspect.Below, binding agent, pigment and thickening material are called " binding agent (Y) ", " pigment (Z) " and " thickening material (W) " respectively.

The content of hollow polymer particle (X2) is 0.5-99.5 weight %, preferred 1-97 weight %, more preferably 3-95 weight %, most preferably 30-70 weight %, based on hollow polymer particle (X2), the summation 100 weight % of binding agent (Y), pigment (Z) and thickening material (W) meter.If the content of hollow polymer particle (X2) is lower than 0.5 weight %, opaqueness, whiteness, degradation such as gloss, inadvisable.If content surpasses 99.5 weight %, the content of binding agent (Y) becomes and is lower than 0.5%, and the particle problems such as powder, accumulation that fall appear in surface strength deficiency like this.And the content of hollow polymer particle (X2) is preferably the 0.8-100 weight part, preferred 20-100 weight part, and more preferably 25-90 weight part, 30-80 weight part most preferably is based on the summation 100 weight part meters of hollow polymer particle (X2) and pigment (Z).

The add-on of binding agent (Y) is preferably the 0.5-99.5 weight % based on component (X2), (Y), (Z) and the summation (W) of 100 weight %, more preferably 1-99 weight %, preferred again 2.5-97 weight %, further more preferably 1-20 weight %, 1-15 weight % most preferably is with solid content meter.If this amount is lower than 0.5 weight %, therefore the particle problems such as powder, accumulation that fall may appear in surface strength deficiency like this.If should amount surpass 99.5 weight %, the blending amount of hollow polymer particle (X2) becomes and is lower than 0.5 weight %, opaqueness like this, the degradation of whiteness and gloss and so on and inadvisable.

The add-on of binding agent (Y) is preferably 1-99 weight %, more preferably 1-20 weight %, and 2.5-18 weight % most preferably is based on component (X2) and the 100 weight part meters of summation (Z) of 100 weight %.

In addition, the add-on of pigment (Z) is preferably below the 99 weight % based on component (X2), (Y), (Z) and the summation (W) of 100 weight %, more preferably below the 89 weight %, and preferred again 20-75 weight %, 30-65 weight % most preferably is with solid content meter.

And the add-on of pigment (Z) is preferably 99.2% following weight, more preferably 80% following weight, and preferred again 10-75 weight %, preferred again 20-70 weight %, 30-65 weight % most preferably is based on component (X2) and the summation (Z) of 100 weight %.

Thickening material (W) is based on the component (X2) of 100 weight %, (Y), (Z) with below the 3 weight % (W), more preferably 0.05-2 weight %, and 0.05-1 weight % most preferably is with solid content meter.

And the add-on of thickening material (W) is preferably below the 5 weight %, and more preferably below the 0.5 weight %, 0.05-2 weight % most preferably is based on component (X2) and the summation (Z) of 100 weight %.

Composition the present invention of the present invention comprises [1] 0.5-99.5 weight % hollow polymer particle (X2), 0.5-99.5 weight % binding agent (Y), with 0-99 weight % pigment (Z) and/or thickening material (W), preferred [2] 0.5-70 weight % hollow polymer particle (X2), 1-15 weight % binding agent (Y), with 0.5-70 weight % pigment (Z) and/or thickening material (W), more preferably [3] 30-70 weight % hollow polymer particle (X2), 1-15 weight % binding agent (Y), with 20-60 weight % pigment (Z) and/or thickening material (W), component (X2) based on 100 weight %, (Y), (Z) and summation (W), with solid content meter.

In this case, if the content of hollow polymer particle (X2) and binding agent (Y) all is based on the 0.5-99.5 weight % of component (X2), (Y), (Z) and the summation (W) of 100 weight %, the content of pigment (Z) and thickening material (W) is respectively 0-99 weight % and 0-3 weight % so.In addition, if the content of hollow polymer particle (X2) and binding agent (Y) is respectively 0.5-70 weight % and 1-15 weight %, the content of pigment (Z) and thickening material (W) is respectively 0.5-70 weight % and 0.05-5 weight % so.In addition, if the content of hollow polymer particle (X2) and binding agent (Y) is respectively 30-70 weight % and 1-15 weight %, the content of pigment (Z) and thickening material (W) is respectively 20-60 weight % and 0.05-5 weight % so.

Various additives can add in the composition of the present invention as dispersion agent, defoamer, water-resisting agent, lubricant, wetting agent, printability improving agent, optical bleaching agent, tinting pigment and dyestuff.

The performance of the White Board that the composition of use second aspect present invention is made under the described condition of embodiment is as follows: gloss; 70-85, print gloss; 79-96, opaqueness; 88-97, whiteness; 80-87, preferred (2) gloss; 74-85, print gloss; 85-96, opaqueness; 90-97, whiteness; 80-87 and more preferably (3) gloss; 81-85, print gloss; 90-96, opaqueness; 91-97, and whiteness; 82-87.

If use its hollow polymer particle (X2), binding agent (Y), pigment (Z) and thickening material (W) content to be respectively 0.5-99.5 weight % based on 100 weight % components (X1), (Y), (Z) and summation (W), 0.5-99.5 weight %, 0-99 weight % and 0-3 weight %, the performance of gained White Board is as follows; Gloss; 70-85, print gloss; 79-96, opaqueness; 88-97, and whiteness; 80-87.

If use its hollow polymer particle (X2), binding agent (Y), pigment (Z), and thickening material (W) content is respectively based on 100 weight % components (X1), (Y), the 0.5-70 weight % of summation (Z) and (W), 1-15 weight %, 0.5-70 weight % and 0.05-5 weight %, the performance of gained White Board can provide as follows: gloss; 74-85, print gloss; 85-96, opaqueness; 90-97, and whiteness; 80-87.

If use its hollow polymer particle (X2), binding agent (Y), pigment (Z) and thickening material (W) content to be respectively 30-70 weight %, 1-15 weight % based on 100 weight % components (X1), (Y), (Z) and summation (W), 20-60 weight % and 0.05-5 weight %, the performance of gained White Board is as follows: gloss; 81-85, print gloss; 90-96, opaqueness; 91-97, and whiteness; 82-87.

Above-mentioned paper coating composition can be directly as the coating composition outside the paper.

3. the manufacture method of White Board and this White Board

White Board of the present invention, comprise body paper and on the single or double of body paper, form and have a coating of hollow polymer particle and binding agent, wherein the hollow rate of hollow polymer particle is 20-99%, preferred 50-99%, more preferably 51-99%, preferred again 56-99%, further more preferably 60-99%, especially preferred 63-98%, especially more preferably 65-98%, especially further more preferably 68-98% and most preferably 70-98%, and average particulate diameter is 200-8000nm, preferred 300-5000nm, more preferably 500-3000nm and preferred again 700-2000nm.

Can be applied to hollow polymer particle (X) in above-mentioned 1 same as before according to hollow polymer particle of the present invention.

Above-mentioned coating can comprise pigment, thickening material etc.Pigment and thickening material can be applied to pigment (Z) and the thickening material (W) in above-mentioned 2 respectively same as before.

Binding agent is a kind of material of be used for boning mutually hollow polymer particle, pigment etc., and it further can be connected to hollow polymer particle and granules of pigments wherein that they contact the place on paper surface.Binding agent constitutes the tack coat in this White Board.Binding agent can be applied to the binding agent (Y) in above-mentioned 2 same as before.This coating can further comprise dispersion agent, defoamer, water repellent agent, lubricant, wetting agent, printability improving agent, optical bleaching agent, tinting pigment and dyestuff.These components itself are identical with above explanation.

White Board of the present invention can be made by the coating composition described in above-mentioned 2 is applied on the body paper.

After the drying, the glue spread of this coating composition is 0.3-30g/m ², preferred 0.5-20g/m ², more preferably 1-15g/m ²If glue spread is lower than 0.3g/m ², the body paper coating is insufficient, like this degradation such as its opaqueness, gloss, whiteness.If glue spread surpasses 30g/m ², it is too big that the coating body becomes, so surface strength descends.

The example of coating process comprises and uses the blade spreader, as the coating process that contacts of short duel spreader, balliduel spreader and excellent blade spreader; The roller spreader is as frame roller spreader, online sizing applicator and metering sizing applicator; With the noncontact coating process that uses airblade coating device, curtain coater, spray applicators etc.

In these methods, consider opaqueness, whiteness, gloss and print gloss, it is especially preferred using the noncontact coating process of curtain coater, spray applicators etc.

In post-processing step, preferably use supercalender, gloss calender, soft-nip calendering machine, gloss press etc. to carry out press polish and handle.Can obtain having excellent glossy White Board like this.

In following preferred embodiment, further describe the present invention, but the invention is not restricted to embodiment.

In the following description, unless refer else, term " part " and symbol " % " are represented weight part respectively " and weight % ".

[1] embodiment 1

(1) comprises the preparation of the aqueous dispersion of seed grain

In the reactor of 2 liters of volumes, add 109.5 parts of water in advance as medium, 0.2 part of Sodium dodecylbenzene sulfonate (trade(brand)name; " F65 " made by flower king (strain)) as emulsifying agent and 0.5 part of Sodium Persulfate as initiators for polymerization.In addition, mix and stir 90 parts of (methyl) methyl acrylates, 10 parts of methacrylic acids, 0.5 part of thiol octyl acetate are as molecular weight regulator, emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)) and 40 parts of water, prepare a kind of aqueous dispersion (i) that comprises monomer mixture.

The aqueous dispersion that comprises monomer mixture (i) of adding 20% in above-mentioned reaction vessel.In the liquid in stirring this reaction vessel, temperature is risen to 75 ℃ with polymerization 1 hour.Then, in 75 ℃ of maintenance temperature, remaining aqueous dispersion (i) was added reaction vessel continuously in 2 hours.In addition, with gains slaking 2 hours, obtain comprising and have solids content 40%, the aqueous dispersion of the seed grain of particle diameter 200nm and weight-average molecular weight 70000 (ii).

(2) comprise the production of the aqueous dispersion of polymer beads (A)

The preparation embodiment that comprises the aqueous dispersion of polymer beads (A) is described as following preparation

Embodiment 1-5.

Preparation embodiment 1

In the reaction vessel of 2 liters of volumes, add 186 parts of water in advance as medium, and to wherein adding above-mentioned seed grain [25 parts the aqueous dispersion that comprises seed grain (ii)] with 10 parts of solid content meters and 0.5 part of Sodium Persulfate as initiators for polymerization.

In addition, mix and stir 69.5 parts of (methyl) methyl acrylates, 30 parts of methacrylic acids, 0.5 part of Vinylstyrene (purity: 55%), 0.1 part of emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)) and 40 parts of water, prepare comprise monomer mixture aqueous dispersion (iii).

Then, in the liquid in stirring this reaction vessel, temperature is risen to 80 ℃ and keep this temperature.The aqueous dispersion that will comprise monomer mixture (iii) added reaction vessel continuously in 3 hours.Then, with gains slaking 2 hours, obtain comprising the aqueous dispersion of the polymer beads A-1 that has particle diameter 410nm and have solids content 31%.

Preparation embodiment 2-5

Polyreaction identical mode according to polymer beads A-1 the time is carried out, and just feeding quantity and monomer component obtain comprising the aqueous dispersion of polymer beads A-2 to A-5 like this according to changing shown in the table 1.

Table 1

Production example	????1-1	????1-2	????1-3	????1-4	????1-5
						Polymer beads	????A-1	????A-2	????A-3	????A-4	????A-5
Seed grain	????10	????3	????17	????10	????10
						Monomer (a-1) methacrylic acid	????30	????30	????30	????10	????50
Monomer (a-2) methyl methacrylate vinyl cyanide SDVB	? ????69.5 ????- ????- ????0.5	? ????69.5 ????- ????- ????0.5	? ????69.5 ????- ????- ????0.5	????59.8 ????10 ????20 ????0.2	? ????18.0 ????- ????30 ????2.0
						Solids content (%)	????31.0	????30.7	????31.2	????31.1	????29.8
Particle diameter (nanometer)	????410	????570	????330	????400	????380
						Polyreaction stability (vision)	????○	????○	????○	????○	????○～△

In table 1, adhere to reaction vessel and the state that stirs on the fan is zero with the polyreaction stability assessment according to aggregate, △ and *.

Zero: the amount of aggregate is few,

△: the amount of aggregate big slightly and

*: the amount of aggregate is big.

(3) production and the assessment of hollow polymer particle (X)

The production example of hollow polymer (X) is described as following examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-5.

Embodiment 1-1

In the reaction vessel of 2 liters of volumes, add 240 parts of water in advance as medium, and to 15 parts of aqueous dispersions (48.4 parts aqueous dispersions) that comprise according to the polymer beads A-1 of above-mentioned preparation that wherein add with solid content meter, 20 parts of vinylbenzene and 0.4 part of Sodium Persulfate are as initiators for polymerization.

In addition, mix and stir 69.5 parts of vinylbenzene, 0.1 part of emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)) and 40 parts of water, prepare and comprise monomeric aqueous dispersion (iv).

Then, in the liquid in the stirring reaction container, temperature is risen to 80 ℃ and kept this temperature polymerizing styrene 30 minutes.Make a kind of vinylbenzene composite polymer particle like this.Subsequently, in the liquid in the stirring reaction container, will comprise the (iv) continuous reaction vessel that adds in 4 hours of monomeric above-mentioned aqueous dispersion under 80 ℃.Begin to add comprise monomeric aqueous dispersion (iv) after 2 hours the time, 0.5 part of vinylformic acid once is fed in the reaction vessel with styrene copolymerized.In addition, comprise after monomeric aqueous dispersion (iv) is fed to reaction vessel all, once be fed to 5 parts of Vinylstyrenes and 5 parts of vinylbenzene in the reaction vessel immediately, obtain a kind of core/shell type polymer beads B1-1, wherein vinylbenzene, vinylformic acid and Vinylstyrene are aggregated the also surface of cover aggregation composition granule A-1.

After all monomer addition finish about 15 minutes, 5 part of 25% ammonium hydroxide under agitation once is fed in the reaction vessel.The temperature of system is risen to 90 ℃, then this system was stirred 2 hours and slaking.Before adding 25% ammonium hydroxide, unreacted monomer (b) is 7% with the weight ratio of whole monomer (b).

Then, to wherein adding 0.3 part of tertbutanol peroxide and 0.1 part of formaldehyde resin, then this compound was stirred 1 hour, obtain a kind of aqueous dispersion, it comprises and has solids content 26.5%, particle diameter 1050nm, internal diameter 860nm and hollow rate are the spherical hollow polymer particle X1-1 of 55% single hole.

Embodiment 1-2 to 1-11 and Comparative Examples 1-1 to 1-5

Hollow polymer particle X1-2 to X1-11 is according to the preparation of the same way as of embodiment 1, and just the content of the unreacted monomer (b) the when kind of polymer beads (A), its amount, monomer (b), rising pH and the Heating temperature after the rising pH are according to changing shown in the table 2.Hollow polymer particle X1-12 to X1-16 is the example outside the scope of hollow polymer particle of the present invention (X), according to table 3, makes according to the same way as of embodiment 1-1.

Because viscosity height, pH raise and heating is at (B1-3) and the solids content (B1-11) is diluted to 18% and carries out afterwards.

Table 2-1

Embodiment		????1-1	???1-2	????1-3	??1-4	??1-5	?1-6
								Polymer beads B		????B1-1	???B1-2	????B1-3	??B1-4	??B1-5	?B1-6
The amount of the polymer beads A polymer beads A that uses		????A-1 ????15	???A-1 ???15	????A-1 ????50	??A-1 ??15	??A-1 ??15	?A-1 ?15
								Monomer (b-1) vinylformic acid methylene-succinic acid		? ????0.5 ????-	? ???0.5 ???-	? ????0.5 ????-	? ??1 ??-	? ??0.5 ??0.5	? ?- ?-
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB GDMA		? ? ????- ????20 ? ? ????69.5 ????- ? ????5 ????5 ????-	? ? ???- ???10 ? ? ???89 ???- ? ???- ???- ???5	? ? ????- ????20 ? ? ????79.5 ????- ? ????- ????- ????-	? ? ??10 ??10 ? ? ??77 ??- ? ??1 ??1 ??-	? ? ??10 ??- ? ? ??72 ??15 ? ??- ??2 ??-	? ? ??- ??20 ? ? ??70 ??- ? ??- ??10 ??-
								Particle diameter (nanometer)		????790	???1110	????570	??790	??760	??750
The Tg of shell polymeric constituent (℃)		????115	???106	????106	??107	??75	??123
								Polyreaction stability (vision)		????○	???○	????○	??○	??○	??○
Hollow polymer particle X		????X1-1	???X1-2	????X1-3	??X1-4	??X1-5	??X1-6
								Polymer beads B		????B1-1	???B1-2	????B1-3	??B1-4	??B1-5	??B1-6
The polymeric reaction temperature of (b) during rising pH (℃)		????90	???85	????80*	??85	??70	??80
								Unreacted monomer content (weight %) in (b) during rising pH		????7	???15	????3	??7	??5	??10
Particle diameter after the processing (nanometer)		????1050	???1220	????890	??1000	??1080	??940
								Diameter of bore after the processing (nanometer)		????860	???800	????786	??810	??930	??750
Degree of hollowness percentage ratio (%)		????55	???28	????69	??53	??64	??51
								Form under the Electronic Speculum	Shape	Spherical
Endoporus	Single hole

*) owing to the viscosity height, pH raises and heating is carried out after solids content is diluted to 18%.

Table 2-2

Embodiment		????1-7	????1-8	????1-9	????1-10	????1-11
							Polymer beads B		????B1-7	????B1-8	????B1-9	????B1-10	????B1-11
The amount of exhausted polymer beads polymer beads A		????A-1 ????15	????A-2 ????15	????A-3 ????15	????A-4 ????15	????A-5 ????15
							Monomer (b-1) vinylformic acid methylene-succinic acid		? ????10 ????-	? ????- ????0.5	? ????5 ????-	? ????5 ????-	? ????0.5 ????-
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB GDMA		? ? ????- ????20 ? ????68 ????- ? ????- ????- ?	? ? ????- ????20 ? ????69.5 ????- ? ????5 ????5 ????-	? ? ????- ????20 ? ????66.5 ????10 ? ????- ????3 ????-	? ? ????- ????20 ? ????59.5 ????- ? ????- ????20 ????-	? ? ????- ????20 ? ????68.5 ????10 ? ????- ????1 ????-
							Particle diameter (nanometer)		????760	????1150	????660	????790	????760
The Tg of shell polymeric constituent (℃)		????108	????114	????88	????120	????85
							Polyreaction stability (vision)		????○	????○	????0	????○	????○～△
Hollow polymer particle X		????X1-7	????X1-8	????X1-9	????X1-10	????X1-11
							Polymer beads B		????B1-7	????B1-8	????B1-9	????B1-10	????B1-11
The polymeric reaction temperature of (b) during rising pH (℃)		????83	????85	????85	????85	????75*
							Unreacted monomer content (weight %) in (b) during rising pH		????20	????10	????7	????7	????5
Particle diameter after the processing (nanometer)		????1010	????1490	????870	????900	????1070
							Diameter of bore after the processing (nanometer)		????830	????1230	????690	????620	????920
Degree of hollowness percentage ratio (%)		????55	????56	????50	????33	????64
							Form under the Electronic Speculum	Shape	Spherical
Endoporus	Single hole

*) owing to the viscosity height, pH raises and heating is carried out after solids content is diluted to 18%.

Table 3

Embodiment		??1-1	???1-2	??1-3	??1-4	??1-5
							Polymer beads B		??B1-12	???B1-13	??B1-14	??B1-15	??B1-16
The amount of exhausted polymer beads A polymer beads A		??A1-1 ??15	???A1-1 ???15	??A1-1 ??15	??A1-1 ??3	??A1-1 ??15
							Monomer (b-1) vinylformic acid methylene-succinic acid		? ??0.5 ??-	? ???0.5 ???-	? ??0.5 ??-	? ??0.5 ??-	? ??0.5 ??-
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB GDMA		? ? ??- ??20 ? ??69.5 ??- ? ??5 ??5 ??-	? ? ???- ???20 ? ???69.5 ???- ? ???5 ???5 ???-	? ? ??- ??1 ? ??88.5 ??- ? ??5 ??5 ??-	? ? ??- ??20 ? ??69.5 ??- ? ??5 ??5 ??-	? ? ??- ??20 ? ??49.5 ??20 ? ??5 ??5 ??-
							Particle diameter (nanometer)		??790	???790	??780	??1320	??800
The Tg of the polymeric constituent of formation shell (℃)		??115	???115	??115	??115	??115
							Polyreaction stability (vision)		??○	???○	??○	??○	??○
Hollow polymer particle X		??X1-12	???X1-13	??X1-14	??X1-15	??X1-16
							Polymer beads B		??B1-12	???B1-13	??B1-14	??B1-15	??B1-16
The polymeric reaction temperature of (b) during rising pH (℃)		??90	???80	??90	??90	??80
							Unreacted monomer content (weight %) during rising pH in (b)		??0	???52	??7	??7	??7
Particle diameter (nanometer) after handling		??850	???850	??1000	??1340	??860
							Diameter of bore (nanometer) after handling		??264	???-	??-	??-	??-
Degree of hollowness percentage ratio (%)		??3	???-	??-	??-	??-
							Form under the Electronic Speculum	Shape	Spherical	Break	Bowl-type	Spherical	Break
Endoporus	Single hole	Do not have	Single hole	Do not have	Do not have

*) owing to the viscosity height, pH raises and heating is carried out after solids content is diluted to 18%

In table 2 and 3, the state that adheres on reaction vessel and the stirring arm according to aggregate is zero with the polyreaction stability assessment, △ and *.

Zero: the amount of aggregate is few,

△: the amount of aggregate big slightly and

*: the amount of aggregate is big.

The appraisal procedure of hollow polymer particle (X) is as follows.

(1) average particulate diameter

Average particulate diameter is by use electron microscope (model under 5000 magnifications; " JSM-6360LA " made by NEC society) observe the particle of 100 random selections and the result's that obtains mean value.

(2) average diameter of bore

Average diameter of bore is by use electron microscope (model under 5000 magnifications; " JSM-6360LA ", make by NEC society) observe the particle of 100 random selections and the result's that obtains mean value.

(3) hollow rate

Use average particulate diameter and average diameter of bore, count particles volume and internal pore volume.Hollow rate is by following formula then, uses the particle volume that calculates and internal pore volume and obtains.

(internal pore volume/particle volume) * 100 (%)

(4) shape of outer shape and endoporus

The shape of outer shape and endoporus is used electron microscope (model under 5000 magnifications; " JSM-6360LA " made by NEC society) observe.

(4) effect of embodiment 1-1 to 1-11 (hollow polymer particle)

Comparative Examples 1-1 is a such example, and wherein the weight ratio of unreacted monomer (b) and whole monomer (b) is lower than 1% when pH raises, and adding all monomers (b) in the time of 2 hours afterwards, pH is raise.Polymerization conversion at monomer (b) surpasses after 99% the particle that does not obtain having enough hollow rate.

Comparative Examples 1-2 is a such example, and wherein the weight ratio of unreacted monomer (b) and whole monomer (b) surpasses 50% when pH raises, and is adding all monomers (b) afterwards, immediately pH is raise, and polymeric reaction temperature is set at 75 ℃.Polymerization conversion at monomer (b) is lower than 50% o'clock rising pH, and fragmentation causes breakage of particles to shell because examining the swelling pressure of part.As a result, do not obtain hollow polymer particle.

Comparative Examples 1-3 is a such example, and wherein at first once reinforced monomer (b-2) is set at below 1/10 with the ratio of polymer beads (A) and nuclear is single face in polymer beads (B).If raise pH under this state, it is inhomogeneous that the thickness of the shell of hollow polymer particle can become.Therefore, after drying, this shell subsides, and obtains bowl-shape particle like this.

Comparative Examples 1-4 is the example below 5 parts that the amount of wherein polymer beads (A) is based on 100 parts of monomers (b).Nuclear is too little owing to expand, and therefore can not obtain enough hollow rate.

Comparative Examples 1-5 is such example, and wherein when polymer beads (B) neutralization and expansion, the temperature of dispersion surpasses the second-order transition temperature (Tg) of the polymkeric substance of the shell that constitutes hollow polymer particle.The fragmentation of this shell, so breakage of particles because examining the swelling pressure partly.As a result, do not obtain hollow polymer particle.

On the other hand, the hollow polymer particle X1-1 to X1-11 among the embodiment 1-1 to 1-11 is spherical hollow particle, has the single hole of enough hollow rate respectively.Polyreaction stability and productive rate when corresponding polyreaction are good.

(5) application on paper coating composition

Embodiment 1-12 to 1-22 and Comparative Examples 1-6 to 1-12

The hollow polymer particle X1-1 to X1-11 that obtains in embodiment 1-1 to 1-11 is used to prepare paper coating composition by following prescription (I).The particle X1-1 that in embodiment 1-1, obtains, X1-12 to X1-16 that in Comparative Examples 1-1 to 1-5, obtains and solid plastic pigment (trade(brand)name; " JSR0640 ', make by JSR company) be used to prepare Comparative Examples 1-6 to 1-12.In order to assess paper coating composition, prepare the multi-disc White Board down in following coating condition (II), then by method (III) the assessment gained scraps of paper.

(I) preparation of paper coating composition

With 0.05 weight % dispersion agent (trade(brand)name; " ARON T-40 " made by East Asia synthetic chemical industry (strain)) and 0.2 weight % dissolution of sodium hydroxide in water.When stirring gained solution, the mineral dye shown in table 4 and 5 is added this solution with the Kores decollator.

After stirring this solution 30 minutes, add the JSR0640 of amount shown in the hollow polymer particle X1-1 to X1-16 of specified amount and the table 4,5 to this solution, as 10 weight % (with solid content meter) copolymer emulsion (trade(brand)names of binding agent; " JSR0619 " made by JSR company) and 3 weight % starch (trade(brand)names; " MS-4600 " made by japanese food (strain)).To wherein adding entry, make that the weight content of all solids is 62 weight %.Like this, make paper coating composition.

Under the situation of Comparative Examples 1-12, the amount of hollow polymer particle X1-1 is set at 0.08 weight % (solids content).

(II) production of White Board

The utilization rod will be as the commercially available thin paper (Zhang Chong: 72g/m of body paper ²) be coated with above-mentioned paper coating composition, make that dry its glue spread afterwards is 15g/m ²(single face), then with gains under 150 ℃ in the gear stove dry 5 seconds.The one-side coated paper of gained is twice " Labo supercalender " (by being made by sharp roller (strain)) through having 40 ℃ of roll surface temperatures under linear pressure 10N/m, obtains a kind of gloss coated paper.

(III) appraisal procedure of White Board

Assess according to following method according to the described White Board of making.The results are shown in table 4 and 5.

(1) does adhesion strength

Use viscosity No.9 printing ink, print several times with RI type printing press.Adhesion attitude on the printing surface is assessed by visual observation.(assessment: the score full marks are 5, and score is big more, and intensity is good more.)

(2) wet adhesion strength

Use RI type printing press, utilize the Morton roller to supply water on the testing plate, carry out one-step print subsequently.Adhesion attitude on the printing surface is assessed by visual observation.(assessment: the score full marks are 5, and score is big more, and intensity is good more.)

(3) gloss

Use mountain, village type glossmeter under input angle 75 degree and reflection angle 75 degree, to measure as yet the not gloss of the White Board of printing.Income value is big more, and gloss is good more.

(4) whiteness

Use blue color filter, use Hunter colorimetry and blancometer to measure the whiteness of White Board.Income value is big more, and whiteness is good more.

(5) opaqueness

Use green color filter, use Hunter colorimetry and blancometer to measure the opaqueness of White Board.Income value is big more, and opaqueness is good more.

(6) thermotolerance

Sample is passed through Labo gloss calender (by being made by sharp roller (strain)) in 180 ℃ of surface temperatures and linear pressure 3N/m next time.Then, measure opaqueness according to the same way as in the item 5.So the difference between the opaqueness of measuring in the opaqueness of measuring and (5) is as the thermotolerance data.Income value is more little, and thermotolerance is good more.

(7) Wang Yan type air infiltration slipperiness

Use the slipperiness of Wang Yan type air infiltration slipperiness instrumentation random sample product.Income value is big more, and slipperiness is big more.

Table 4-1

Embodiment		?????1-12	??1-13	????1-14	????1-15	????1-16
							Hollow particle X	Component	?????X1-1	??X1-2	????X1-3	????X1-4	????X1-5
Amount (part)	??10??????8.8	??10	????10	????10	????10
						Inorganic based pigment Z (part)		The one-level clay *1The secondary clay *2Lime carbonate *3	??30 ??30 ??30	??30 ??30 ??30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30
Amount to	??90????(79.6)		????90	????90	????90
							The summation of X1 and Z (part)		??100	??100	????100	????100	????100
Binding agent Y (part)	JSR0619 starch MS4600	??10 ??3	??10 ??3	????10 ????3	????10 ????3	????10 ????3
							Amount to	??13????(11.5)	??13	????13	????13	????13
	X, the summation of Z and Y (part)		??113???(100.0)	??113	????113	????113							????113
The physicals of White Board							Do adhesion	??????4.2	??4.3	????4.2	????4.5	????4.7
	Wet adhesion	??????4.3	??4.4	????4.3	????4.5	????4.4
							Gloss	??????78.2	??76.1	????80.1	????78.5	????79.3
	Opaqueness	??????92.4	??90.3	????94.3	????92.1	????93.8
							Thermotolerance (opaqueness drop-out value)	??????0.5	??1.2	????4.4	????1.2	????1.4
	Whiteness	??????84.3	??82.3	????85.6	????84.5	????85.0
							Wang Yan formula slickness	??????3420	??3320	????3690	????3570	????3600

* 1: trade(brand)name; " UW-90 " made by EMC company limited

* 2: trade(brand)name; " HS " made by Huer company limited

* 3: trade(brand)name; " Calpital 90 " are made by ECC company limited

Table 4-2

Embodiment		????1-17	????1-18	????1-19	????1-20	????1-21	????1-22
								Hollow polymer particle X	Component	????X1-6	????X1-7	????X1-8	????X1-9	????X1-10	????X1-11
Amount (part)	????10	????10	????10	????10	????10	????10
							Inorganic based pigment Z (part)		The one-level clay *1The secondary clay *2Lime carbonate *3	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30
Amount to	????90	????90	????90	????90	????90	????90
								The summation of X1 and Z (part)		????100	????100	????100	????100	????100	????100
Binding agent Y (part)	JSR0619 starch MS4600	????10 ????3	????10 ????3	????10 ????3	????10 ????3	????10 ????3	????10 ????3
								Amount to	????13	????13	????13	????13	????13	????13
	X, the summation of Z and Y (part)		????113	????113	????113	????113	????113								????113
The physicals of White Board								Do adhesion	????4.3	????4.8	????4.2	????4.1	????4.3	????4.2
	Wet adhesion	????4.6	????4.3	????4.5	????4.3	????4.6	????4.2
								Gloss	????78.3	????78.4	????78.9	????77.1	????76.4	????79.7
	Opaqueness	????92.0	????92.3	????92.9	????91.9	????90.5	????93.7
								Thermotolerance (opaqueness drop-out value)	????0.8	????1.4	????0.4	????1.3	????0.2	????1.5
	Whiteness	????83.2	????84.4	????84.6	????84.2	????82.1	????85.2
								Wang Yan type slickness	????3430	????3420	????3450	????3390	????3310	????3590

* 1: trade(brand)name; " UW-90 " made by EMC company limited

* 2: trade(brand)name; " HS " made by Huer company limited

* 3: trade(brand)name; " Calpital 90 " are made by ECC company limited

Table 5

Comparative Examples		????1-6	????1-7	????1-8	????1-9	????1-10	????1-11	????????1-12
									Hollow polymer particle X	Component	????X1-12	????X1-13	????X1-14	????X1-15	????X1-16	???JSR0640	????????X1-1
Amount (part)	??10?????(8.8)	????10	????10	????10	????10	????10	????0.08????(0.08)
								Inorganic based pigment Z (part)		The one-level clay *1The secondary clay *2Lime carbonate *3	??30 ??30 ??30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30	????30 ????30 ????30
Amount to	??90?????(79.6)	????90	????90	????90	????90	????90	????90??????(87.31)
									The summation of X1 and Z (part)		??100	????100	????100	????100	????100	????100	????90.08
Binding agent Y (part)	JSR0619 starch MS4600	??10 ??3	????10 ????3	????10 ????3	????10 ????3	????10 ????3	????10 ????3	????10 ????3
									Amount to	??13?????(11.5)	????13	????13	????13	????13	????13	????13??????(12.61)
	X, the summation of Z and Y (part)		??113.0??(100.0)	????113.0	????113.0	????113.0	????113.0	????113.0									????113.1???(100.00)
The physicals of White Board									Do adhesion	???????3.7	????3.9	????3.6	????3.5	????3.9	????4.6	?????????4.3
	Wet adhesion	???????3.2	????3.8	????3.4	????3.1	????3.4	????4.7	?????????4.2
									Gloss	???????69.1	????67.2	????69.9	????68.2	????67.7	????65.3	?????????60.1
	Opaqueness	???????89.1	????88.4	????89.3	????88.9	????88.5	????86.4	?????????86.5
									Thermotolerance (opaqueness drop-out value)	???????3.1	????3.2	????2.6	????3.1	????3.9	????5.4	?????????0.3
	Whiteness	???????82.2	????81.1	????82.8	????82.0	????82.5	????80.1	?????????78.8
									The Wang Yan slickness	???????2990	????2890	????2990	????2910	????2880	????2740	?????????2560

* 1: trade(brand)name; " UW-90 " made by EMC company limited

* 2: trade(brand)name; " HS " made by Huer company limited

* 3: trade(brand)name; " Calpital 90 " are made by ECC company limited

(6) effect of embodiment 1-12 to 1-22 (White Board)

Comparative Examples 1-61-12 is such example, wherein uses the hollow polymer particle of making by the manufacture method outside the scope of the invention.Their performance is as follows: do adhesion strength; 3.7-3.9, wet adhesion strength; 3.1-3.8, gloss; 67.2-69.9, opaqueness; 88.4-89.3, thermotolerance; 2.6-3.9, whiteness; 81.1-82.8 and Wang Yan type slipperiness; 2880-2990.Therefore, bad as the White Board performance.

Comparative Examples 1-11 is such example, and wherein using is not that the known polymer particle of hollow is as polymer beads.In this case, above-mentioned performance is as follows: do adhesion strength; 4.6, wet adhesion strength; 4.7, and thermotolerance; 5.4, good relatively, but gloss; 65.3, opaqueness; 86.4, whiteness; 80.1 and Wang Yan type slipperiness; 2740.Therefore, bad as the performance balance of White Board.

Comparative Examples 1-12 is such example, wherein uses the hollow polymer particle X1-1 that makes by an example of production technique of the present invention, but the content of hollow polymer particle is lower than 0.1% (that is, 0.08%).In this case, above-mentioned performance is as follows: do adhesion strength; 4.3 and wet adhesion strength; 4.2, better relatively, but gloss; 60.1, opaqueness; 86.5, thermotolerance; 0.3, whiteness; 78.8 and Wang Yan type slipperiness; 2560.Therefore, the performance balance of White Board is bad.

On the other hand, embodiment 1-12 to 1-22 is the example that wherein uses coating composition, wherein comprises the hollow polymer particle X1-1 to X1-11 that makes by an example of production technique of the present invention respectively of specified amount.In this case, above-mentioned performance is as follows: do adhesion strength; 4.2-4.8, wet adhesion strength; 4.2-4.6, gloss; 76.4-80.1, opaqueness; 90.3-94.3, thermotolerance; 0.2-4.4, whiteness; 82.3-85.6 and Wang Yan formula slipperiness; 3310-3690.Therefore, the performance balance of White Board is excellent.

[2] embodiment 2

(1) comprises the preparation of the aqueous dispersion of seed grain

In the reaction vessel of 2 liters of volumes, add 109.5 parts of water in advance as medium, 0.2 part of Sodium dodecylbenzene sulfonate (trade(brand)name; " F65 " made by flower king (strain)) as emulsifying agent and 0.5 part of Sodium Persulfate as initiators for polymerization.

In addition, mix and stir 90 parts of (methyl) methyl acrylates, 10 parts of methacrylic acids, 0.5 part of thiol octyl acetate as molecular weight regulator, emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)) and 40 parts of water, prepare the aqueous dispersion that comprises monomer mixture.

The monomeric aqueous dispersion of adding 20% in above-mentioned reaction vessel.In the liquid in the stirring reaction container, temperature is risen to 75 ℃ with polymerization 1 hour.Then, in 75 ℃ of maintenance temperature, the residual monomers aqueous dispersion was added reaction vessel continuously in 2 hours.In addition, with gains slaking 2 hours, obtain comprising and have solids content 40%, the aqueous dispersion of the seed grain of particle diameter 200nm and weight-average molecular weight 70000.

(2) comprise the production of the aqueous dispersion of polymer beads (A)

The preparation embodiment of the aqueous dispersion that comprises polymer beads (A) is below described.

In the reaction vessel of 2 liters of volumes, add 186 parts of water in advance as medium, and to wherein adding above-mentioned seed grain (25 parts the aqueous dispersions that comprise seed grain) with 10 parts of solid content meters and 0.5 part of Sodium Persulfate as initiators for polymerization.

In addition, mix and stir 69.5 parts of (methyl) methyl acrylates, 30 parts of methacrylic acids, 0.5 part of Vinylstyrene (purity: 55%), 0.1 part of emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)) and 40 parts of water, prepare the aqueous dispersion that comprises monomer mixture.

Then, in the time of with the liquid in the stirring reaction container, temperature is risen to 80 ℃ and keep this temperature.The aqueous dispersion that will comprise monomer mixture added reaction vessel continuously in 3 hours.Then, with gains slaking 2 hours, obtain a kind of aqueous dispersion that comprises the polymer beads A-1 that has particle diameter 410nm and have solids content 31%.

(3) production and the assessment of hollow polymer particle (X)

Polymer beads (B) is made according to the same way as of the foregoing description 1, and hollow polymer particle (X) is made by using polymer beads (B).The preparation embodiment of hollow polymer particle of the present invention is described as following examples 2-1 to 2-14.

Embodiment 2-1

In the reaction vessel of 2 liters of volumes, add 300 parts of water in advance as medium, and to the aqueous dispersion (51.6 parts aqueous dispersions) of comprising that wherein adds with 16 parts of solid content meters according to the above-mentioned polymer beads A-1 that makes, 10 parts of vinylbenzene as the monomer (b-2) that once adds and 0.4 part of Sodium Persulfate as initiators for polymerization.

In addition, mix and stir the monomers (b-2) of 69.5 parts of continuous addings of vinylbenzene conduct, 0.1 part of emulsifying agent (trade(brand)name; " F65 " made by flower king (strain)), 0.5 part of vinylformic acid is as monomer (b-1) and 40 parts of water, prepares to comprise monomeric aqueous dispersion (v).

Then, in the liquid in the stirring reaction container, temperature is risen to 80 ℃ and keep this temperature, polymerizing styrene 30 minutes.Obtain a kind of vinylbenzene composite polymer particle like this.Subsequently, in the liquid in the stirring reaction container, (v) in 4 hours, add continuously reaction vessel will comprising monomeric above-mentioned aqueous dispersion under 80 ℃.In addition, comprise monomeric aqueous dispersion (after v) being fed to reaction vessel all, immediately 20 parts of vinylbenzene are once added reaction vessel to obtain a kind of core/shell type polymer beads B2-1, wherein vinylbenzene and vinylformic acid are aggregated the also surface of cover aggregation composition granule A-1.The particle diameter of polymer beads B2-1 is 810nm.

After all monomer addition finish about 3 minutes, 2 part of 25% ammonium hydroxide (8 parts of solution) under agitation once is fed in the reaction vessel.This system was stirred 21 o'clock and slaking.Before adding 25% ammonium hydroxide, unreacted monomer (b) is 9% with the weight ratio of whole monomer (b).

Then, to wherein adding 0.3 part of tertbutanol peroxide and 0.1 part of formaldehyde resin, then this compound is stirred 1 hour obtaining a kind of aqueous dispersion, it comprises and has solids content 23.3%, the spherical hollow polymer particle X2-1 of particle diameter 1100nm and internal diameter 930nm.

Embodiment 2-2 to 2-14

Just change the amount and the kind of polymer beads (A-1) and monomer (b), make polymer beads B2-2 to B2-14 in embodiment 2-3 and 2-9, hollow polymer particle is made according to the same way as of embodiment 2-1, just with (B2-3) and the solids content (B2-9) be diluted to 18% in its pH of adjusting, to heat-treat, and other hollow polymer particle is made according to the same way as of embodiment 2-1, just according to unreacted monomer (b) content and the Heating temperature that change shown in the table 6 when regulating pH.

Table 6-1

Embodiment		??2-1	??2-2	???2-3	??2-4	??2-5
							Polymer beads B		??B2-1	??B2-2	???B2-3	??B2-4	??B2-5
The amount of exhausted polymer beads A polymer beads A		??A-1 ??16	??A1-1 ??10	???A-1 ???20	??A-1 ??16	??A-1 ??16
							Monomer (b-1) vinylformic acid methylene-succinic acid		? ??0.5 ??-	? ??0.5 ??-	? ???1 ???-	? ??0.5 ??-	? ??0.5 ??0.5
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB AMS		? ? ??- ??10 ? ??69.5 ??- ? ??20 ??- ??-	? ? ??- ??10 ? ??59.5 ??- ? ??30 ??- ??-	? ? ???- ???20 ? ???69 ???- ? ???10 ???- ???-	? ? ??- ??10 ? ??69.5 ??- ? ??10 ??10 ??-	? ? ??- ??10 ? ??69 ??- ? ??10 ??10 ??-
							Particle diameter (nanometer)		??810	??890	???750	??810	??820
The Tg of shell (℃)		??104	??104	???104	??110	??110
							Polyreaction stability (vision)		??○	??○	???○	??○	??○
Hollow polymer particle X		??X2-1	??X2-2	???X2-3	??X2-4	??X2-5
							Polymer beads B		??B2-1	??B2-2	???B2-3	??B2-4	??B2-5
The polymeric reaction temperature of (b) during rising pH (℃)		??80	??90	???80	??85	??85
							Unreacted monomer content (weight %) during rising pH		??9	??20	???5	??11	??11
Particle diameter (nanometer) after handling		??1100	??1190	???1100	??1150	??1160
							Diameter of bore (nanometer) after handling		??960	??1010	???1060	??1020	??1030
Degree of hollowness percentage ratio (%)		??66	??61	???89	??70	??70
							The thickness of shell (nanometer)		??140	??180	???40	??130	??130
Form under the Electronic Speculum	Shape	Spherical
							Endoporus	Single hole

Table 6-2

Embodiment		??2-6	???2-7	??2-8	??2-9	??2-10
							Polymer beads B		??B2-6	???B2-7	??B2-8	??B2-9	??B2-10
The amount of exhausted polymer beads A polymer beads A		??A-1	???A-1	??A-1	??A-1	??A-1
							??16	???16	??16	??16	??16
		Monomer (b-1) vinylformic acid methylene-succinic acid		? ??0.5 ??0.5	? ???0.5 ???0.5	? ??0.5 ??-						? ??0.5 ??-	? ??0.5 ??-
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB AMS							? ? ??- ??- ? ??69.5 ??- ? ??10 ??- ??10	? ? ???10 ???10 ? ???59.5 ???- ? ???10 ???- ???10	? ? ???- ???10 ? ???69.5 ???- ? ???10 ???- ???10	? ? ??- ??10 ? ??59.5 ??10 ? ??10 ??- ??10	? ? ??- ??10 ? ??89.5 ??- ? ??- ??- ??-
		Particle diameter (nanometer)		??810	???810	???810						??810	??810
The Tg of shell (℃)							??107	???107	???107	??107	??104
		Polyreaction stability (vision)		??○	???◎	???○						??◎	??○
Hollow polymer particle X							??X2-6	???X2-7	???X2-8	??X2-9	??X2-10
		Polymer beads B		??B2-6	???B2-7	???B2-8						??B2-9	??B2-10
The polymeric reaction temperature of (b) during rising pH (℃)							??80	???80	???80	??80	??90
		Unreacted monomer content (weight %) during rising pH		??13	???13	???13						??13	??3
Particle diameter (nanometer) after handling							??1150	???1180	???1180	??1180	??1000
		Diameter of bore (nanometer) after handling		??1030	???1080	???1070						??1100	??820
Degree of hollowness percentage ratio (%)							??72	???77	???75	??81	??55
		The thickness of shell (nanometer)		??120	???100	???110						??80	??180
Form under the Electronic Speculum	Shape						Spherical
		Endoporus	Single hole

Table 6-3

Embodiment		????2-11	????2-12	????2-13	????2-14
						Polymer beads B		????B2-11	????B2-12	????B2-13	????B2-14
The amount of exhausted polymer beads A polymer beads A		????A-1 ????16	????A-1 ????10	????A-1 ????10	????A-1 ????5
						Monomer (b-1) vinylformic acid methylene-succinic acid		? ????0.5 ????-	? ????0.5 ????0.5	? ????0.5 ????-	? ????0.5 ????-
Monomer (b-2) [monomer that at first once adds] styrene-methyl methacrylate [the aqueous dispersion monomer that adds continuously] styrene-acrylonitrile copolymer acid butyl ester [the final monomer that once adds] SDVB AMS		? ? ????- ????20 ? ????69.5 ????- ? ????10 ????- ????-	? ? ????- ????10 ? ????79 ????- ? ????5 ????5 ????-	? ? ????- ????20 ? ????69.5 ????- ? ????5 ????- ????5	? ? ????- ????20 ? ????49.5 ????20 ? ????5 ????- ????5
						Particle diameter (nanometer)		????800	????830	????830	????850
The Tg of shell (℃)		????104	????110	????104	????75
						Polyreaction stability (vision)		????○	????○	????○	????○
Hollow polymer particle X		????X2-11	????X2-12	????X2-13	????X2-14
						Polymer beads B		????B2-11	????B2-12	????B2-13	????B2-14
The polymeric reaction temperature of (b) during rising pH (℃)		????80	????80	????90	????80
						Unreacted monomer content (weight %) during rising pH		????7	????8	????7	????7
Particle diameter (nanometer) after handling		????990	????1100	????1100	????1150
						Diameter of bore (nanometer) after handling		????830	????820	????800	????890
Degree of hollowness percentage ratio (%)		????59	????41	????38	????46
						The thickness of shell (nanometer)		????160	????280	????300	????260
Microscopically	Shape	Spherical
						Form	Endoporus	Single eight holes

*) owing to the viscosity height, pH raises and heating is carried out after solids content is diluted to 18%.

In table 6, adhere to reaction vessel and the state that stirs on the fan is zero with the polyreaction stability assessment according to aggregate, △ and *.

Zero: the amount of aggregate is few,

△: the amount of aggregate big slightly and

*: the amount of aggregate is big.

The average particulate diameter of gained hollow polymer particle, average diameter of bore, hollow rate, outer shape and interior hole shape are assessed by above-mentioned [1] method.

The average particulate diameter of hollow polymer particle X2-1 to X2-14 is the 990-1190 nanometer.The average diameter of bore of hollow polymer particle X2-1 to X2-14 is the 800-1100 nanometer.The hollow rate of hollow polymer particle X2-1 to X2-9 is that 61-89% and X2-10 to X2-14 are 38-59%.

And all hollow polymer particle X2-1 to X2-14 are the spherical hollow particles that has single hole respectively.

(4) as the application of paper coating composition

Paper coating composition by method preparation shown below prepares White Board, estimates.

Embodiment 2-15 to 2-26 and Comparative Examples 2-1 to 2-8

With 0.05 weight % dispersion agent (trade(brand)name; " ARON T-40 " made by the East Asia synthetic chemical industry) and 0.2 weight % dissolution of sodium hydroxide in water.When stirring gained solution, the mineral dye shown in table 7 and 8 is added this solution with the Kores decollator.Mineral dye in the table 7 and 8 is identical with the foregoing description 1.

After adding mineral dye, dispersion was stirred 30 minutes.Again to every kind of hollow polymer particle X2-1 to X2-14 shown in the amount of wherein further adding shown in table 7 and 8 and table 7 and 8, have the copolymer emulsion (trade(brand)name: " JSR0619 ", make) and the starch (trade(brand)name of solids content 48% by JSR (strain); " MS-4600 " made by japanese food (strain)) as binding agent (Y), and thickening material (trade(brand)name; " Modico1 VD-S " made by Sannopco company).To wherein adding entry, make that the total solids level that is called " colour solid content " is the value shown in table 7 and 8.Prepare paper coating composition like this.Value in table 7 and 8 the parenthesis is the total amount of hollow polymer particle (X), binding agent (Y), pigment (Z) and thickening material (W) therein amount with solid content meter when being set at 100 parts.

Comparative Examples 2-1 to 2-5 wherein uses hollow rate to be lower than the example of 60% hollow polymer particle X2-10 to X2-14.Comparative Examples 2-6 is a such example, based on the summation of hollow polymer particle (X2), binding agent (Y), pigment (Z) and the thickening material (W) of 100 weight parts, wherein the content with the hollow polymer particle (X2) of solid content meter is lower than 0.5 weight part (referring to table 8).In addition, Comparative Examples 2-7 is a such example, wherein, be lower than 0.5 weight part (referring to table 8) based on the summation of hollow polymer particle (X2), binding agent (Y), pigment (Z) and the thickening material (W) of 100 weight parts with the content of the binding agent (Y) of solid content meter.

Comparative Examples 2-9

Paper coating composition is made according to the same way as of embodiment 2-15 to 2-26 and Comparative Examples 2-1 to 2-8, only is to use the polymer beads (trade(brand)name that is not hollow; " JSR0640 " made by JSRCorp.) as polymer beads.

Comparative Examples 2-10

Paper coating composition is made according to the same way as of embodiment 2-15 to 2-26 and Comparative Examples 2-1 to 2-8, only is to use hollow rate to be lower than 60% polymer beads (trade(brand)name; " JSRAE850 " made by JSR (strain)) as polymer beads.

Table 7-1

Embodiment		??????2-15	???????2-16	?????2-17	??????2-18
						Hollow polymer particle X	Component	??????X2-1	???????X2-2	?????X2-3	??????X2-4
Content (part)	5????????(4.5)	????5??????(4.5)	??1???????(0.9)	??3???????(2.6)
					Inorganic based pigment Z (part)		One-level clay secondary clay lime carbonate	35???????(31.2) 30???????(26.7) 30???????(26.7)	????35?????(31.3) ????30?????(26.8) ????30?????(26.8)	??39??????(33.9) ??30??????(26.0) ??30??????(26.0)	??27??????(23.1) ??0????????0 ??70??????(59.8)
Amount to	95???????(84.7)	????95?????(84.8)	??99??????(85.9)	??97??????(82.9)
						The summation of X and Z (part)		100??????(89.1)	????100????(89.3)	??100?????(86.8)	??100?????(85.5)
Binding agent Y (part)	JSR0619 starch MS4600	12???????(10.7) 0?????????0	????9??????(8.0) ????3??????(2.7)	??15??????(13.0) ??0???????0	??14??????(12.0) ??3???????(2.6)
						Amount to	12???????(10.7)	????12?????(10.7)	??15??????13.0	??17??????(14.5)
	Thickening material (part)	????Modicaol?VD-S	0.2??????(0.2)	????0??????0	??0.2?????(0.2)						??17??????(14.5)
All summations (part)						112.2????(100.0)	????112.2??(100.0)	??115.2???(100.0)	??1172????(100.0)
		Coloring solid content (%)		??????60.0	????????55.0					??????60.0	???????55.0
Glue spread (g/m 2)						??????10.0	????????15.0	??????10.0	???????7.0
		The physicals of White Board	Do adhesion	??????4.3	????????4.0					??????4.6	???????4.5
Wet adhesion	??????4.4					????????4.1	??????4.2	???????4.5
			Gloss	??????78.3	????????77.1				??????80.4	???????76.4
Print gloss	??????88.3					????????87.2	??????89.0	???????87.3
			Opaqueness	??????92.2	????????92.0				??????91.9	???????92.1
Whiteness	??????84.4					????????84.2	??????83.1	???????84.3
			The Wang Yan slickness	??????3440	????????3350				??????3500	???????3300

Table 7-2

Embodiment		??????2-19	????2-20	?????2-21	????2-22
						Hollow polymer particle X	Component	??????X2-5	????X2-6	?????X2-7	????X2-8
Amount (part)	????50????(44.2)	1????????(0.9)	??100????(86.8)	20???????(17.8)
					Inorganic based pigment Z (part)		One-level clay secondary clay lime carbonate	????0?????0 ????0?????0 ????50????(44.2)	39???????(34.8) 30???????(26.7) 30???????(26.7)	??0???????0 ??0???????0 ??0???????0	20???????(17.8) 30???????(26.7) 30???????(26.7)
Amount to	????50????(44.2)	99???????(88.2)	??0???????0	80???????(71.3)
						The summation of X1 and Z (part)		????100???(88.4)	100??????(89.1)	??100????(86.8)	100??????(89.1)
Binding agent Y (part)	JSR0619 starch MS4600	????12????(10.6) ????1?????(0.9)	12???????(10.7) 0????????0	??15?????(13.0) ??0???????0	12???????(10.7) 0?????????0
						Amount to	????13????(11.5)	12???????(10.7)	??15?????(13.0)	12???????(10.7)
	Thickening material (part)	????Modicaol?VD-S	????0.1????(0.1)	0.2??????(0.2)	??0.2????(0.2)						0.2??????(0.2)
All summations (part)						????113.1??(100.0)	112.1????(100.0)	??115.2??(100.0)	112.2????(100.0)
		Coloring solid content (%)		?????????45.0	????62.0					??????23.0	?????55.0
Glue spread (g/m 2)						?????????3.0	????19.0	??????1.0	?????5.0
		The physicals of White Board	Do adhesion	?????????4.3	????4.2					??????4.9	?????4.2
Wet adhesion	?????????4.4					????4.8	??????4.4	?????4.5
			Gloss	?????????82.9	????78.4				??????75.4	?????78.9
Print gloss	?????????91.0					????91.1	??????89.3	?????88.3
			Opaqueness	?????????94.2	????92.0				??????91.7	?????92.9
Whiteness	?????????84.3					????83.2	??????85.2	?????84.6
			Wang Yan type slickness	?????????4090	????3400				??????3100	?????3460

Table 7-3

Embodiment		????2-23	????2-24	????2-25	????2-26
						Hollow polymer particle X	Component	????X2-9	????X2-1	????X2-1	????X2-1
Amount (part)	??40????(38.8)	100???????(88.3)	70???????(60.8)	3????????(3.0)
					Inorganic based pigment Z (part)		One-level clay secondary clay lime carbonate	??10????(9.7) ??0?????0 ??50????(48.4)	0?????????0 0?????????0 0?????????0	0?????????0 0?????????0 30???????(26.0)	0?????????0 0?????????0 0?????????0
Amount to	??60????(58.1)	0?????????0	30???????(26.0)	0?????????0
						The summation of X and Z (part)		??100???(96.9)	100?????(88.3)	100??????(86.8)	3????????(3.0)
Binding agent Y (part)	JSR0619 starch MS4600	??3?????(2.9) ??0?????0	13??????(11.5) 0?????????0	15???????(13.0) 0?????????0	3????????(3.0) 96.8?????(96.8)
						Amount to	??3?????(2.9)	13??????(11.5)	15???????(13.0)	99.8?????(99.8)
	Thickening material (part)	????Modicaol?VD-S	?0.2????(0.2)	0.2?????(0.2)	0.2??????(0.2)						0.2??????(0.2)
All summations (part)						103.2???(100.0)	113.2???(100.0)	115.2????(100.0)	103.0????(100.0)
		Coloring solid content (%)		????65.0	????23.0					????30.0	????30.0
Glue spread (g/m 2)						????19.0	????1.0	????6.0	????10.0
		The physicals of White Board	Do adhesion	????4.4	????4.7					????4.9	????5.0
Wet adhesion	????4.4					????4.9	????4.2	????5.0
			Gloss	????83.0	????76.4				????83.9	????75.1
Print gloss	????92.1					????88.3	????92.0	????95.3
			Opaqueness	????92.4	????91.9				????93.7	????90.0
Whiteness	????83.1					????85.1	????84.4	????82.9
			Oken type slickness	????4200	????3300				????4300	????5800

Table 8-1

Comparative Examples		????2-1	????2-2	???2-3	???2-4	???2-5
							Hollow polymer particle X	Component	????X2-10	????X2-11	???X2-12	???X2-13	???X2-14
Amount (part)	5???????(4.5)	5??????(4.5)	5???????(4.5)	5??????(4.5)	5??????(4.5)
						Inorganic based pigment Z (part)		One-level clay secondary clay lime carbonate	35??????(31.2) 30??????(26.7) 30??????(26.7)	35?????(31.2) 30?????(26.7) 30?????(26.7)	35??????(31.2) 30??????(26.7) 30??????(26.7)	35?????(31.2) 30?????(26.7) 30?????(26.7)	35?????(31.2) 30?????(26.7) 30?????(26.7)
Amount to	95??????(84.7)	95?????(84.7)	95??????(84.7)	95?????(84.7)	95?????(84.7)
							The summation of X and Z (part)		100?????(89.1)	100????(89.1)	100?????(89.1)	100????(89.1)	100????(89.1)
Binding agent Y (part)	JSR0619 starch MS4600	????12 ??(10.7) 0????????0	????12 ??(10.7) 0???????0	????12 ??(10.7) 0????????0	????12 ??(10.7) 0???????0	????12 ??(10.7) 0??????0
							Amount to	12??????(10.7)	12?????(10.7)	12??????(10.7)	12?????(10.7)	12?????(10.7)
	Thickening material (part)	????Modicao1?VD-S	0.2?????(0.2)	0.2????(0.2)	0.2?????(0.2)	0.2????(0.2)							0.2????(0.2)
All summations (part)							112.2???(100.0)	112????(100.0)	112.2???(100.0)	112.2??(100.0)	112????(100.0)
		Coloring solid content (%)		????60.0	????60.0	????60.0						????60.0	????60.0
Glue spread (g/m 2)							????10.0	????10.0	????10.0	????10.0	????10.0
		The physicals of White Board	Do adhesion	????4.3	????4.2	????4.3						????4.4	????4.3
Wet adhesion	????4.4						????4.3	????4.4	????4.2	????4.4
			Gloss	????68.5	????69.3	????65.4					????62.1	????66.3
Print gloss	????75.3						????76.3	????72.3	????70.3	????73.3
			Opaqueness	????87.5	????87.7	????86.5					????85.4	????87.0
Whiteness	????80.2						????81.0	????79.8	????78.8	????80.2
			Oken type slickness	????2890	????2940	????2790					????2770	????2800

Table 8-2

Comparative Examples		????2-6	????2-7	????2-8	??2-9	??2-10
							Hollow polymer particle X	Component	????X2-1	????X2-1	????X2-1	??JSR0640	??JSRAE850
Amount (part)	0.5????(0.4)	100?????(99.4)	100????(88.3)	5???????(4.5)	5??????(4.5)
						Inorganic based pigment Z (part)		One-level clay secondary clay lime carbonate	39?????(35.2) 30?????(26.7) 30?????(26.7)	0???????0 0???????0 0???????0	0???????0 0???????0 0???????0	35??????(31.2) 30??????(26.7) 30??????(26.7)	35?????(31.2) 30?????(26.7) 30?????(26.7)
Amount to	99.5???(88.7)	0???????0	0???????0	95??????(84.7)	95?????(84.7)
							The summation of X and Z (part)		100????(89.1)	100????(99.4)	100????(88.3)	100?????(89.1)	100????(89.1)
Binding agent Y (part)	JSR0619 starch MS4600	12?????(10.7) 0??????0	0.4????(0.4) 0???????0	13?????(11.5) 0???????0	12??????(10.7) 0????????0	12?????(10.7) 0???????0
							Amount to	12?????(10.7)	0.4????(0.4)	13?????(11.5)	12???????(10.7)	12?????(10.7)
	Thickening material (part)	????Modicaol?VD-S	0.2????(0.2)	0.2????(0.2)	0.2????(0.2)	0.2??????(0.2)							0.2????(0.2)
All summations (part)							112.2??(100.0)	100.6??(100.0)	113.2??(100.0)	112.2????(100.0)	112.2??(100.0)
		Coloring solid content (%)		????62.0	????23.0	????23.0						????60.0	????60.0
Glue spread (g/m 2)							????19.0	????1.0	????0.2	????10.0	????10.0
		The physicals of White Board	Do adhesion	????4.5	????1.5	????5.0						????4.6	????4.2
Wet adhesion	????4.8						????1.6	????5.0	????4.8	????4.9
			Gloss	????60.4	????75.6	????55.3					????58.6	????67.0
Print gloss	????68.3						????78.2	????62.8	????67.3	????75.3
			Opaqueness	????84.3	????91.7	????80.3					????83.2	????87.3
Whiteness	????77.9						????85.3	????76.7	????76.6	????80.0
			Wang Yan type slickness	????2710	????3460	????2520					????2680	????2820

(1) production of White Board

Utilize " Labo curtain coater " (model; " spreader FL-S3G flows " made by Anest rock field (strain)) will be under surface covered 100m/s as the commercially available thin paper (Zhang Chong: 72g/m of body paper ²) be coated with every kind of paper coating composition with embodiment 2-15 to 2-26 and Comparative Examples 2-1 to 2-10, make that the glue spread after the dry said composition is the value shown in table 7 and 8, subsequently with gains under 150 ℃ in the gear stove dry weight 3 seconds.With gained one-side coated paper twice " Labo supercalender " (by making) under linear pressure 10N/m, obtain a kind of gloss coated paper by sharp roller Corp. through having 40 ℃ of roll surface temperatures.In Comparative Examples 2-8, the glue spread of paper coating composition after drying is lower than 0.3g/m ²

(2) assessment of White Board

Be evaluated at the dried adhesion strength of the White Board that obtains in (1), wet adhesion strength, gloss, print gloss, whiteness, opaqueness and Wang Yan type air and soak into slipperiness, the results are shown in Table 7 and 8.Dried adhesion strength, wet adhesion strength, gloss, whiteness, opaqueness and Wang Yan type air soak into slipperiness to be assessed by aforesaid method.Print gloss is assessed by the following method.

[method of assessment print gloss]

Utilize viscosity No.9 printing ink, RI type printing press is used to print.After ink setting, the gloss on the printing surface uses mountain, village type glossmeter to measure under input angle 75 degree and reflection angle 75 degree.Income value is big more, and print gloss is good more.

(5) effect of embodiment 2-12 to 2-26 (White Board)

Use is not that the polymer beads of hollow is lower than 60% polymer beads (Comparative Examples 2-1 to 2-5,2-9 and 2-10) as polymer beads or use hollow rate, obtains following result: gloss; 58.6-68.5, print gloss; 67.3-73.3, opaqueness: 83.2-87.7 and whiteness; 76.6-81.0.Performance is not good.

Total amount in binding agent (Y) (solids content), pigment (Z) and thickening material (W) is 100 parts, and the amount of pigment (Z) is lower than under 0.5 part the situation and (referring to table 8, obtains following result: gloss therein; 60.4, print gloss; 68.3, opaqueness; 84.3 and whiteness; 77.9.The respective performances deficiency.

On the other hand, if hollow rate is more than 60% and the content of hollow polymer particle is (Comparative Examples 2-7 and embodiment 2-15-2-26) more than 0.5%, obtain following result: gloss; 75.1-83.9, print gloss; 78.2-95.3, opaqueness; 90.0-94.2, and whiteness; 82.9-85.20 respective performances excellence.

Especially, be 100 parts in the total amount of hollow polymer particle (X) and pigment (Z), hollow polymer particle (X) is that 40-70 part and pigment (Z) they are (embodiment 2-19,2-23 and 2-25) under the situation of 30-60 part therein, obtains following result: gloss; 82.9-83.9, print gloss 91.0-92.1, opaqueness; 92.4-94.2 and whiteness; 83.1-84.4.These performances and balance thereof are very good.

In addition, the total amount of binding agent (Y) (solids content), pigment (Z) and thickening material (W) is 100 parts of meters, and the amount of binding agent (Y) is lower than under 0.5 part the situation therein, does not obtain enough dried adhesion strengths and wet adhesion strength.But the amount more than 0.5 part (embodiment 2-15 to 2-26) shows excellent dried adhesion strength 4.0-5.0 and wet adhesion strength 4.1-5.0 respectively.

Even should measure within the scope of the invention, if glue spread is lower than 0.3g/m ²(Comparative Examples 2-8) can not obtain enough gloss, print gloss, opaqueness and whiteness.If but glue spread is 0.3g/m ²More than (embodiment 2-15-2-26), gloss, print gloss, opaqueness and whiteness are excellent.

Claims (18)

1. the manufacture method of a hollow polymer particle comprises:

The emulsion polymerization step of preparation polymer beads (A), polymerization is by the monomer (a) that can form with the free radical polymerization monomer (a-2) (total amount of above-mentioned (a-1) and above-mentioned (a-2) is set at 100 weight %) of above-mentioned unsaturated carboxylic acid (a-1) copolymerization of the unsaturated carboxylic acid (a-1) of 5-80 weight % and 20-95 weight %

The emulsion polymerization step of preparation core/shell type polymer beads (B), at 5-1, the part of polymerization 100 weight parts monomers (b) under the existence of the described polymer beads of 000 weight part (A), its unsaturated carboxylic acid by 0-20 weight % (b-1) and 80-100 weight % can form with the free radical polymerization monomer (b-2) (total amount of described (b-1) and described (b-2) is set at 100 weight %) of described unsaturated carboxylic acid (b-1) copolymerization, obtain polymer beads (B) thus, the surface coverage of wherein said polymer beads (A) has the shell of the unreacted monomer component that comprises the polymeric constituent that obtains by the described monomer of a polymerization part (b) and described monomer (b)

Expansion step will comprise the above step of pH regulator to 7 of the dispersion of described polymer beads (B) with volatile alkali, neutralize like this and expand above-mentioned polymer beads (B) and

The step of the described unreacted monomer component of polymerization.

2. according to the manufacture method of the hollow polymer particle of claim 1, wherein said polymeric constituent and the weight ratio of described unreacted monomer component in described shell are 99/1-50/50.

3. according to the manufacture method of the hollow polymer particle of claim 1, wherein said shell is by at first once adding the described monomer (b) that part or all will become described polymeric constituent, and letex polymerization subsequently should reinforced monomer and make.

4. according to the manufacture method of the hollow polymer particle of claim 3, in 100 weight %, more than 50% weight of all described monomers (b) esters of unsaturated carboxylic acids and/or ethene aromatic substance in its described monomer (b) that once adds.

5. according to the manufacture method of the hollow polymer particle of claim 3, the wherein said monomer (b) that once adds is 10/1-1/10 with the weight ratio of described polymer beads (A).

6. according to the manufacture method of the hollow polymer particle of claim 1, wherein said free radical polymerization monomer (b-2) comprises the crosslinkable free radical polymerization monomer, and the content of described crosslinkable free radical polymerization monomer is 100 weight timing all described free radical polymerization monomers (b-2), is below 50% weight.

7. according to the manufacture method of the hollow polymer particle of claim 1, the temperature of wherein said dispersion when described polymer beads (B) is neutralized and expands is set in below the second-order transition temperature (Tg) of described polymeric constituent.

8. according to the manufacture method of the hollow polymer particle of claim 1, wherein said emulsion polymerization passes through the only described free radical polymerization monomer of polymerization (b-2), and after the described monomer of 10-35 weight % (b-2) polymerization, remaining described free radical polymerization monomer of polymerization (b-2) and described unsaturated carboxylic acid (b-1) carry out.

9. the hollow polymer particle of making by the manufacture method of claim 1.

10. according to the hollow polymer particle of claim 9, its hollow rate is 50-99%.

11. a paper coating composition is characterized in that comprising the hollow polymer particle according to claim 9 (X) and 0-99.9 weight % pigment (Z) and/or the binding agent (Y) of 0.1-100 weight %, in described (X), (Y) and the 100 weight % of total amount (Z).

12. according to the paper coating composition of claim 11, the hollow rate of wherein said hollow polymer particle (X) is 50-99%.

13. a paper coating composition is characterized in that comprising the hollow polymer particle with hollow rate 50-99% and average particulate diameter 300-5000nm.

14. according to the paper coating composition of claim 13, the thickness of the shell of wherein said hollow polymer particle is 30-200nm.

15. according to the paper coating composition of claim 13, wherein said hollow polymer particle is the hollow particle of claim 9 record.

16. according to the paper coating composition of claim 13, in total component 100 weight %, the described hollow polymer particle of 0.5-99.5 weight %, 0.5-99.5 weight % binding agent and 0-99 weight % pigment and/or thickening material are with solid content meter.

17. White Board, the coating that comprises body paper and form on the single or double of described body paper and be made of hollow polymer particle and binding agent, the hollow rate that it is characterized in that described hollow polymer particle is that 50-99% and average particulate diameter are 300-5000nm.

18. the manufacture method of a White Board is characterised in that the paper coating composition according to claim 13 record is applied on the body paper, makes that the glue spread of described composition after the said composition drying is 0.3-30g/m ²