CN100554352C - The preparation method of the nanometer aqueous automobile paint of scrape resistant - Google Patents

The preparation method of the nanometer aqueous automobile paint of scrape resistant Download PDF

Info

Publication number
CN100554352C
CN100554352C CNB2006101173094A CN200610117309A CN100554352C CN 100554352 C CN100554352 C CN 100554352C CN B2006101173094 A CNB2006101173094 A CN B2006101173094A CN 200610117309 A CN200610117309 A CN 200610117309A CN 100554352 C CN100554352 C CN 100554352C
Authority
CN
China
Prior art keywords
nano
powder
linking agent
water
agent
Prior art date
Application number
CNB2006101173094A
Other languages
Chinese (zh)
Other versions
CN1970663A (en
Inventor
施利毅
张清涛
张震宇
杭建忠
徐夏章
Original Assignee
上海大学
江门市银帆化学有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海大学, 江门市银帆化学有限公司 filed Critical 上海大学
Priority to CNB2006101173094A priority Critical patent/CN100554352C/en
Publication of CN1970663A publication Critical patent/CN1970663A/en
Application granted granted Critical
Publication of CN100554352C publication Critical patent/CN100554352C/en

Links

Abstract

The present invention relates to the preparation method of the water nano car paint that a kind of scrape resistant, anti-stone hit, belong to chemistry painting industry fabricating technology field.The present invention combines the environmental protection characteristic of the low VOC of water-borne coatings with the small-size effect of nanoparticle, the character of surface effects, prepare the water-borne coatings of scrape resistant.Water-borne coatings of the present invention has following composition and weight percent: coating film forming base-material 60~70%, nano-powder 5~15%, aqueous solvent 20~25%, auxiliary agent 0.5~1.0%; Auxiliary agent has thickening material, dispersion agent, defoamer, film coalescence aid; Adopt linking agent in addition, its consumption is benchmark with the nano-composite emulsion, and its ratio is 0.9: 1~1: 1; Linking agent is mainly the chemical substance of trimeric cyanamide system.Index is hindered in the scratch resistance of paint coatings can reach for 96~99% (representing with gloss retention).

Description

The preparation method of the nanometer aqueous automobile paint of scrape resistant

Technical field

The present invention relates to a kind of preparation method of nanometer aqueous automobile paint of scrape resistant, belong to chemistry painting industry fabricating technology field.

Background technology

Body of a motor car scribbles one deck paint film, plays protection and decorative effect, but during use, vehicle body regular meeting and hard objects contact-impact.For example automobile is subjected to the bump of stone chippings on the road in the process of moving; When scrubbing vehicle body, impurity washing away in the water to paint film; Be subjected to the scratch of objects such as metal, branch in addition, thereby influenced the attractive in appearance of body of a motor car.

Simultaneously, along with car paint towards environmental protectionization, the water-borne coatings with low VOC becomes one of main flow of following car paint.Therefore, exploitation has the important topic that water-borne coatings that excellent, damage resistant, anti-stone hit becomes the car paint scientific research personnel.

Have quantum effect and the surface effects that big specific surface area and very strong interfacial interaction produce by dried nano-powder, nano material is not only shown be different from general macroscopical performance of composites; Also may have characteristic performance and function that stock blend does not possess.Nano material is used in the coating, can improve the mechanical property of paint film, can keep the higher transparency simultaneously.

The higher car paint of development scratch resistance, traditional method is the development of new resin.According to the literature, people such as U.S. Van Der Linde once developed the higher car paint of a kind of scratch resistance, and this coating is to be filmogen with the vibrin, mixes varnish and colored paint, and its scoring resistance is 89~95%.But its manufacturing cost is higher, and the performance biography does not reach desirable requirement.

Summary of the invention

The objective of the invention is to overcome the defective of existing automotive coating, water nano car paint that a kind of scrape resistant, anti-stone hits and preparation method thereof is provided.

The nanometer aqueous automobile paint of a kind of scrape resistant of the present invention is characterized in that this water-borne coatings has following composition and weight percent:

Coating film forming base-material, 60~70%; Include urethane acrylate, epoxy acrylate, urethane and polyester, select wherein any;

Nano-powder, 5~15%; Include silicon-dioxide, titanium dioxide, barium sulfate, barite, lime carbonate and aluminum oxide, select wherein any; The particle diameter of nano-powder is 20~80nm;

Aqueous solvent, 20~25%; Be deionized water;

Auxiliary agent, 0.5~1.0%; Comprise thickening material, dispersion agent, defoamer, film coalescence aid; Select wherein more than three kinds or three kinds;

Make nano-composite emulsion by above component;

Linking agent is a benchmark with the nano-composite emulsion that makes, and the part by weight of its add-on is 0.9: 1~1: 1; Linking agent includes hexa methoxy melamine methylol, butylation trimeric cyanamide, isobutyl trimeric cyanamide, blended methylates and the butylation trimeric cyanamide; Select wherein any.

The preparation method of the nanometer aqueous automobile paint of a kind of scrape resistant of the present invention is characterized in that having following technological process and step:

A. by the ready raw material of above-mentioned formula rate, at first nano-powder is put into container, add dispersion agent, part defoamer and certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards;

B. above-mentioned nano-powder dispersion liquid slurry is incorporated in the resinous polymer of coating film forming base-material, the defoamer that adds film coalescence aid and remainder subsequently mixes, and disperses 30 minutes with homogenizer again, makes nano-composite emulsion;

C. then linking agent is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.9: 1~1: 1; Under 25~30 ℃ of temperature, mix, and add remaining solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Advantage of the present invention is: its VOC content of the raw material of employing is low, meets the environmental requirement of car paint, and is water-borne coatings, and is easy to use; The car paint that the inventive method makes has good scratch resistance, anti-stone hits performance; Its scratch resistance or scoring resistance are represented with protecting the light rate, can be reached 96~99%.

Embodiment

After now specific embodiments of the invention being described in.

Embodiment 1

The compositing formula of Xuan Ding car paint at first, wherein: coating film forming base-material urethane acrylate consumption is 70%, and the nano-powder amount of titanium is 8%, and the solvent deionized water consumption is 21%, and auxiliary dosage is 1%.

The titanium dioxide that is averaged particle diameter 40nm is put in the container, name is gone into dispersion agent TENLO 70, defoamer polydimethylsiloxane subsequently, and the certain amount of solvent deionized water carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards; This nano-powder dispersion liquid slurry is incorporated in the coating film forming base-material urethane acrylate, the defoamer polydimethylsiloxane that adds film coalescence aid Texanol alcohol ester and part remainder subsequently mixes, disperseed again 30 minutes with homogenizer, make nano-composite emulsion; Then linking agent hexa methoxy melamine methylol is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.01: 1; Under 28 ℃ of temperature, mix, and add remaining partial solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Made coating evenly is sprayed on the tinplate, and being coated with thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets the precoating plate Sample A, gives over to benchmark test.

Embodiment 2

Selected system component prescription is substantially with above-mentioned embodiment 1 in the present embodiment.But nano-powder adopts the titanium dioxide of 60nm, and its consumption is 12wt%, and the consumption of film forming base-material urethane acrylate is 66wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step.

Final prepared coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets the precoating plate sample B, gives over to benchmark test.

Embodiment 3

The compositing formula of at first selected good car paint, wherein: coating film forming base-material urethane acrylate consumption is 70%, and nano-powder silicon-dioxide consumption is 8%, the solvent deionized water consumption is 21%, auxiliary dosage is 1%.

The silicon-dioxide that is averaged particle diameter 40nm is put in the container, add dispersion agent TENLO 70, defoamer polydimethylsiloxane, certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards; This nano-powder dispersion liquid slurry is incorporated in the coating film forming base-material urethane acrylate, the defoamer polydimethylsiloxane that adds film coalescence aid Texanol alcohol ester and part remainder subsequently mixes, disperseed again 30 minutes with homogenizer, make nano-composite emulsion; Then linking agent butylation melamine is added in the above-mentioned nano-composite emulsion that makes; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.91: 1; Under 28 ℃ of temperature, mix, and add surplus partial solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.

Made coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample C, gives over to benchmark test.

Embodiment 4

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the silicon-dioxide of 40nm, and its consumption is 12wt%, and the film forming base-material adopts epoxy acrylate, and its consumption is 66wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide, and the linking agent of adding and the part by weight of emulsion are 0.91: 1.

Finally make nanometer aqueous automobile paint.Obtained coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample D, gives over to benchmark test.

Embodiment 5

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barium sulfate of 50nm, and its consumption is 8%, and the film forming base-material adopts epoxy acrylate, and its consumption is 70wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, is 0.91: 1 but linking agent adopts isobutyl trimeric cyanamide, the linking agent of adding and the part by weight of emulsion.

Finally make nanometer aqueous automobile paint.Obtained coating evenly is sprayed on the tinplate, and coating thickness is 25 ± 5 μ m, toasts 30 minutes down at 60 ℃, gets precoating plate sample E, gives over to benchmark test.

Embodiment 6

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barite of 40nm, and its consumption is 10wt%, and the film forming base-material adopts epoxy acrylate, and its consumption is 68wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts the butylation trimeric cyanamide.

Finally make nanometer aqueous automobile paint.Make precoating plate sample F by above-mentioned with quadrat method, give over to benchmark test.

Embodiment 7

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the barite of 60nm, and its consumption is 15wt%, and the film forming base-material adopts urethane, and its consumption is 63wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide.

Finally make nanometer aqueous automobile paint.Make precoating plate sample G by above-mentioned with quadrat method, give over to benchmark test.

Embodiment 8

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the aluminum oxide of 40nm, and its consumption is 11wt%, and the film forming base-material adopts polyester, and its consumption is 67wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts the hexa methoxy melamine methylol, and the linking agent of adding and the part by weight of emulsion are 1: 1.

Finally make nanometer aqueous automobile paint.Made coating is made precoating plate sample H by above-mentioned with quadrat method.

Embodiment 9

Compositing formula selected in the present embodiment is substantially with above-mentioned embodiment 1, but nano-powder adopts the lime carbonate of 50nm, and its consumption is 11wt%, and the film forming base-material adopts polyester, and its consumption is 67wt%.The preparation process of present embodiment is fully identical with the foregoing description 1 with step, and different is that linking agent adopts blended to methylate and the butylation trimeric cyanamide, and the linking agent of adding and the part by weight of emulsion are 0.91: 1.

Finally make nanometer aqueous automobile paint.Made coating is made precoating plate sample I by above-mentioned with quadrat method.

Benchmark test

1. do scratch resistance

On the Clear coating of sample board, be coated with Bon Ami abrasive material thin layer (this abrasive material is by the supply of Faultloss Starch/BonAmi company), put exceedingly beautiful felt fingerstall subsequently, prop up the contact sample board, come and go 10 times wiping examination, to test its scratch situation.Scratch resistance is that promptly gloss guarantor percentage is represented by the regional relative not relative ratios of the glossiness at 20 ° of visual angles in scratch zone of the scratch of measuring paint sheet.

2. wet scratch resistance

Adopt above-mentioned similar program, just substitute Bon Ami abrasive material with wet oxidation aluminium slurry.This aluminum oxide slurry is made up of AMP 95% aqueous solution and 7 parts of aluminum oxide (120# grit) of 294 parts of deionized waters, 21 parts of ASE-60 thickening materials, 25 parts of amino methyl propyl alcohol.

Test result sees the following form 1.

The performance evaluation result of each coating model of table 1

Test event Conventional ??A ??B ??C ??D ??E ??F ??G ??H ??I Do scratch resistance (gloss retention %) ??82% ??97% ??93% ??94% ??92% ??93% ??93% ??90% ??88% ??89% Wet scratch resistance (gloss retention %) ??71% ??83% ??79% ??81% ??78% ??79% ??80% ??77% ??75% ??76% 20 ° of gloss ??85 ??98 ??94 ??95 ??94 ??94 ??95 ??93 ??92 ??92

By experimental result as seen, compare, hit performance through the scoring resistance of nano-material modified aqueous clear coating coating and anti-stone and be significantly increased with the conventional paint coatings that does not add the nano powder body.

Claims (2)

1. the nanometer aqueous automobile paint of a scrape resistant is characterized in that this water-borne coatings has following composition and weight percent:
Coating film forming base-material, 60~70%; Include urethane acrylate, epoxy acrylate, urethane and polyester, select wherein any;
Nano-powder, 5~15%; Include silicon-dioxide, titanium dioxide, barium sulfate, barite, lime carbonate and aluminum oxide, select wherein any; The particle diameter of nano-powder is 20~80nm;
Aqueous solvent, 20~25%; Be deionized water;
Auxiliary agent, 0.5~1.0%; Comprise thickening material, dispersion agent, defoamer, film coalescence aid; Select wherein more than three kinds or three kinds;
Make nano-composite emulsion by above component;
Linking agent is a benchmark with the nano-composite emulsion that makes, and the part by weight of its add-on is 0.9: 1~1: 1;
Linking agent includes hexa methoxy melamine methylol, butylation trimeric cyanamide, isobutyl trimeric cyanamide, blended methylates and the butylation trimeric cyanamide; Select wherein any.
2. the preparation method of the nanometer aqueous automobile paint of the described a kind of scrape resistant of claim 1 is characterized in that having following technological process and step:
A. by the ready raw material of above-mentioned formula rate, at first nano-powder is put into container, add dispersion agent, part defoamer and certain amount of solvent deionized water subsequently, carried out pre-dispersed 10 minutes through homogenizer, with high speed vibrating machine vibration 1 hour, make the nano-powder dispersion liquid afterwards;
B. above-mentioned nano-powder dispersion liquid slurry is incorporated in the resinous polymer of coating film forming base-material, the defoamer that adds film coalescence aid and remainder subsequently mixes, and disperses 30 minutes with homogenizer again, makes nano-composite emulsion;
C. then linking agent is added in the above-mentioned nano-composite emulsion that has made; The linking agent that adds and the part by weight of above-mentioned emulsion are 0.9: 1~1: 1; Under 25~30 ℃ of temperature, mix, and add remaining solvent deionized water at any time, regulate viscosity, promptly make nanometer aqueous automobile paint to 20S.
CNB2006101173094A 2006-10-19 2006-10-19 The preparation method of the nanometer aqueous automobile paint of scrape resistant CN100554352C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006101173094A CN100554352C (en) 2006-10-19 2006-10-19 The preparation method of the nanometer aqueous automobile paint of scrape resistant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006101173094A CN100554352C (en) 2006-10-19 2006-10-19 The preparation method of the nanometer aqueous automobile paint of scrape resistant

Publications (2)

Publication Number Publication Date
CN1970663A CN1970663A (en) 2007-05-30
CN100554352C true CN100554352C (en) 2009-10-28

Family

ID=38111696

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006101173094A CN100554352C (en) 2006-10-19 2006-10-19 The preparation method of the nanometer aqueous automobile paint of scrape resistant

Country Status (1)

Country Link
CN (1) CN100554352C (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100954799B1 (en) * 2007-12-28 2010-04-28 에이케이켐텍 주식회사 Coating solution of non-orient electrical steel sheet, method for coating non-orient electrical steel sheet using the same, and coating film of non-orient electrical steel sheet
EP2277961A1 (en) * 2009-07-02 2011-01-26 Sika, S.A.U. Acrylic-polyurethane polymer coating dispersions for roofing
CN101845217B (en) * 2010-05-11 2011-12-07 陕西科技大学 Preparation method of water-based polyurethane/nano-silicon dioxide composite emulsion
CN102153928B (en) * 2011-02-28 2012-11-28 重庆恒美涂料有限公司 Aqueous glass paint and preparation method thereof
CN102876216A (en) * 2012-09-26 2013-01-16 苏州汾湖电梯有限公司 Coating for aluminum alloy decoration panel of elevator
CN103602181A (en) * 2013-10-20 2014-02-26 安徽嘉木橡塑工业有限公司 Automobile finishing varnish
CN103897467B (en) * 2014-04-17 2017-04-19 任国华 Primer and preparation method thereof
CN104073154A (en) * 2014-07-27 2014-10-01 广西梧州龙鱼漆业有限公司 Wear-resisting undercoat composite
CN105364188B (en) * 2015-12-10 2017-12-08 太仓贝斯特机械设备有限公司 Copper bar stripping machine guide pipe
CN105368213A (en) * 2015-12-10 2016-03-02 太仓贝斯特机械设备有限公司 Dustproof scraping-resistant aluminum rod
CN106085184A (en) * 2016-08-17 2016-11-09 安徽江淮车轮有限公司 A kind of fork truck steel ring wear-resistant paint
CN106085183A (en) * 2016-08-17 2016-11-09 安徽江淮车轮有限公司 A kind of steel ring wheel green environmental friendly coatings
CN106752586A (en) * 2016-12-26 2017-05-31 十堰福波新材料有限公司 A kind of automobile water base stone-impact-proof paint of high thixotropic and preparation method
CN106800848A (en) * 2017-01-23 2017-06-06 清远嘉信涂料有限公司 A kind of bloom automobile coating
CN106928839A (en) * 2017-03-07 2017-07-07 沈阳宣伯新材料科技有限公司 The long-acting resistance to sand washing high-iron carriage shell waterborne metallic paint of high durable
CN108250888A (en) * 2017-12-23 2018-07-06 陈建峰 A kind of preparation method of shock resistance anticorrosion type car paint

Also Published As

Publication number Publication date
CN1970663A (en) 2007-05-30

Similar Documents

Publication Publication Date Title
CN104910779B (en) A kind of super-hydrophobic Acrylic Polyurethane Coating and preparation method thereof
CN100368489C (en) Coating compositions with modified particles and methods of using the same
EP2292702B1 (en) Exterior paint formulation
CN101765642B (en) Metallic paint, method for the production thereof, and use thereof
CN101166798B (en) Coating compositions providing improved mar and scratch resistance and methods of using the same
CN1777699B (en) Method for coating metallic surfaces with a composition that is rich in silane
ES2425415T3 (en) Black resin composition that dissipates heat excellently, a method for treating a zinc coated steel sheet using this composition and steel sheet treated in this way
KR101202887B1 (en) Composition containing crystalline cellulose composite
US8709145B2 (en) Aqueous coating composition with corrosion resistant thin-coat aluminum pigments, method for production and use thereof
DE602004002633T2 (en) Chromium-free agent for the treatment of metal surfaces
TW402629B (en) Water-reducible coating composition for providing corrosion protection, and use and preparations thereof
CN1315872C (en) Usage of carboxymethyl cellulose acetate butyrate
ES2641844T3 (en) Coating compositions that include magnesium hydroxide and related coated substrates
Müller et al. Coatings formulation
CN101157813B (en) Electroplating effect imitated plastic paint and preparation method, diluent and process of using same
US4937274A (en) Coating composition
JP5665549B2 (en) Aqueous coating composition, process for its production and use thereof
ES2252939T3 (en) Method for the formation of a coating film and composition of the coating.
EP2473569B1 (en) Adhesive agent for coatings on different substrate surfaces
JP5174313B2 (en) Aqueous pigment pastes containing metal pigments and their use for the production of water-based coatings that impart effects
ES2350198T3 (en) Coating compositions that have improved accession, coated substrates and procedures related to themselves.
CN104629268B (en) Have special decorative effects exempts from spraying polymer blend and its preparation method and application
TWI242587B (en) Conductive, organic coatings
US4450200A (en) Coating composition and coated article
EP2421924B1 (en) Water-free high-solids base paints, the production thereof and the use thereof for producing multilayer paint coatings, and multilayer paint coatings comprising a base coating made of a water-free high-solids base paint

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP01 Change in the name or title of a patent holder

Address after: 200444 Baoshan District Road, Shanghai, No. 99

Co-patentee after: Guangdong Yinfan Chemistry Co., Ltd.

Patentee after: Shanghai University

Address before: 200444 Baoshan District Road, Shanghai, No. 99

Co-patentee before: Jiangmen Yinfan Chemical Co., Ltd.

Patentee before: Shanghai University

ASS Succession or assignment of patent right

Free format text: FORMER OWNER: GUANGDONG YINFAN CHEMISTRY CO., LTD.

Effective date: 20140130

Owner name: GUANGDONG YINFAN CHEMISTRY CO., LTD.

Free format text: FORMER OWNER: SHANGHAI UNIVERSITY

Effective date: 20140130

COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 200444 BAOSHAN, SHANGHAI TO: 529060 JIANGMEN, GUANGDONG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20140130

Address after: 529060 Guangdong province Jiangmen Yinfan Jianghai District Industrial Park Road, Xinmin

Patentee after: Guangdong Yinfan Chemistry Co., Ltd.

Address before: 200444 Baoshan District Road, Shanghai, No. 99

Patentee before: Shanghai University

Patentee before: Guangdong Yinfan Chemistry Co., Ltd.

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20140414

Address after: Muenster

Patentee after: BASF coating Co., Ltd.

Address before: 529060 Guangdong province Jiangmen Yinfan Jianghai District Industrial Park Road, Xinmin

Patentee before: Guangdong Yinfan Chemistry Co., Ltd.

ASS Succession or assignment of patent right

Owner name: BASF COATING GMBH

Free format text: FORMER OWNER: GUANGDONG YINFAN CHEMISTRY CO., LTD.

Effective date: 20140414